CN106735300B - A kind of synthetic method of ultra-thin silver nanoparticle plate - Google Patents
A kind of synthetic method of ultra-thin silver nanoparticle plate Download PDFInfo
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Abstract
The present invention is the synthetic method of ultra-thin silver nanoparticle plate, and this method includes：The seed-solution of crystal seed type highly consistentization is prepared by the way that a large amount of and excessive hydrogen peroxide and strong reductant are added into the mixed solution of silver nitrate and surfactant；Using seed-solution, by controlling the amount of reducing agent and silver nitrate in reaction process, it is controllable to obtain pattern, size, and the first monodispersed silver nanoparticle plate；Second of silver nanoparticle plate with random " gap " and " hot spot " is obtained by taking turns continuous growth more；By introducing halide ion/hydrogen peroxide etching defect, more continuous growths of wheel obtain the smooth superelevation draw ratio in edge, super large and the third ultra-thin silver nanoparticle plate；And the nano-plates by wrapping up above-mentioned three kinds of unique structures, obtain the ultra-thin silver nanoparticle plate of nucleocapsid.The present invention creatively proposes a kind of preparation method of the nanometer harden structure with random " gap " and " hot spot "；Solve the problems, such as that silver nanoparticle plate material stability is poor.
Description
Technical field
The present invention relates to nanophotonics, phasmon, infrared optics, nano material, printed electronic and thin-film devices
Field, the more particularly to synthesis of ultra-thin silver nanoparticle plate and size, morphological control method.
Background technology
Silver nanoparticle plate is a kind of special two-dimension nano materials, has unique physics, chemical property.Especially in optics side
Face has surface phasmon (SPs) effect.In illumination, the electronics and incident light of silver nanoparticle plate surface free vibration are mutual
Effect forms resonance, generates the local electromagnetic wave transmitted along surface.Its property has close ties with scantling.
Width has local surface etc. at several nanometers to the small size silver nanoparticle plate between tens nanometer in visible light wave range
From plasmon resonance effect (LSPR), local optical intensity density can be caused substantially to enhance by light field local around particle.In size and
Pattern in the case of monodispersed, the resonance absorbing peak of silver nanoparticle plate solution be it is unimodal, peak value with the increase of nanometer board size and
Red shift causes macroscopical sample to have a series of different colors such as Huang, orange, plum, purple, indigo plant.Importantly, sample monodisperse degree
Better, the halfwidth of resonance absorbing peak is narrower.On this basis, the small size nano-plates of high yield are composable forms the thin of macroscopic view
Membrane module, by the size for adjusting nano-plates, you can realize the accuracy controlling of local light distribution.In addition to thin-film device, small ruler
Very little silver nanoparticle plate is also widely used for printed electronic field, makes electrically conductive ink.Some researches show that same size is led
Line, by silver nanoparticle board group at sample 4 orders of magnitude smaller than the sample resistance that silver nanoparticle ball forms, can effectively reduce the electricity of conducting wire
Resistance.This is because metal particle size is smaller, atom it is more living more, be more suitable as electrically conductive ink, and silver nanoparticle plate is two dimension
Anisotropic nano material, size in a thickness direction is only several nanometers, is much smaller than the nano particle of other various patterns.
Therefore, silver nanoparticle plate is easier to form welding effect between each other, and then forms block materials, therefore conductivity is significantly higher than it
The conducting wire that his pattern nano particle is formed.And with the promotion of nano-plates yield, thinner, the nanometer in ink of nano-plates
The homogenization of grain morphological regions, the resistance of the conducting wire and electronic device that are printed can also further decrease, and performance can also significantly improve.
It is metal nano material and device arts in conclusion preparing the ultra-thin monodisperse silver nanoparticle plate of high yield, small size
One research focus can solve the bottleneck problem of above-mentioned various application fields.
The synthetic method of existing small size silver nanoparticle plate has：Photo-reduction, electrochemical process, supercritical ultrasonics technology etc., this
A little method periods length, low yield, need to improve yield by purifying.Crystal seed growth method is by by the generation of crystal seed in contrast
It is separated with growth course, according to the condition of the requirement of different times kinetics control reaction, from pattern, size can be obtained
Controllable silver nanoparticle plate sample.But sample prepared by existing crystal seed method, mostly there is very a high proportion of spherical shape in final product
Particle cannot achieve monodispersed silver nanoparticle plate.Its main bottleneck is that the crystal seed that initial reaction stage generates cannot be screened fully,
The crystal seed type generated is various, including single crystal seed and twin crystal seed etc., and different types of crystal seed is obtained by continuous growth
Granule-morphology is different, to directly affect the raising of yield.Therefore, it is badly in need of introducing more efficient Filtering system, realizes brilliant
Highly consistentization of type.Highly consistentization of crystal seed can also make the controllability enhancing of continuous growth work simultaneously, can be improved
Solution concentration, acquisition yield is high, concentration high crystalline is good, size adjustable silver nanoparticle plate.
Size is at hundreds of nanometers to large-sized nano-plates between some tens of pm, surface plasmon resonance (SPR)
Peak can red shift to mid and far infrared, even terahertz wave band, be formed in infrared and terahertz wave band new opplication.Therefore, it develops
Go out large-sized silver nanoparticle plate, can fill up these wave bands can use the blank of surface plasmons metal nano plate material.Meanwhile
Size is a kind of important sub-wavelength optical waveguide transmission medium in hundreds of nanometers to some tens of pm of large-sized silver nanoparticle plate.By
There is surface phasmon effect in silver nanoparticle plate, light local can be propagated in sub-wavelength spatial, the pattern hot spot of formation is remote
Less than traditional Medium Wave Guide, optical diffraction limit is broken through, the integrated level of photonic device is greatly improved, is to realize the next generation
The key raw material of ultralarge scale integration photon chip system.The large scale silver nano material of mono-crystalline structures is inherently a kind of
The two-dimensional waveguide of high quality can transmit subwavelength information on two dimensional surface.Meanwhile it if being introduced on large scale silver nanoparticle plate
Special sub-wavelength structure forms " hot spot ", can also scatter in space subwavelength information, can also further strengthen light and object
Interaction between matter, this will be that people are breaking through diffraction limit, probe under meso-scale between light and substance
The physics law of interaction provides new technical method.Therefore, the silver nanoparticle plate of large scale smooth surface and surface are repaiied
Decorations, generate the large scale silver nanoparticle plate of hot spot, there is important application prospect in field of nanometer technology.
At this stage, this large area and large-sized silver nanoparticle film are prepared mainly by traditional coating technique, using
The processes such as photoetching, etching are shaped.This method and process is complicated, of high cost, and the silver nanoparticle film produced is
Amorphous, scattering effect is apparent when electronics and photon transmit wherein, and loss is very big, and prepared device performance is low, Bu Nengman
The actual application requirement of foot.Therefore researchers propose the Yin Na with chemically synthesized monocrystalline and size more than a few micrometers of magnitudes
Rice plate, instead of silver nanoparticle film prepared by film deposition techniques, as the raw material for preparing metal waveguide device.But existingization
The silver nanoparticle plate of method synthesis, for thickness generally at 100 nanometers or more, thinner large-sized silver nanoparticle plate there is no passing through of method
Method prepares, and also cannot be satisfied existing requirement on devices.Theoretical research shows only when the thickness of silver nanoparticle plate is reduced to
When 20 ran, transmission loss just can significantly reduce, and meet the requirement of practical nanometer waveguide device.Therefore for solve etc. from
The loss problem of excimer waveguide device improves device performance, and there is an urgent need to invent that large scale, ultra-thin silver nanoparticle plate can be prepared
Chemical synthesis process.
Invention content
Technical problem：The purpose of the invention is to overcome the shortcoming of prior art, it is proposed that a kind of ultra-thin silver is received
The synthetic method of rice plate realizes the highly consistentization sieve of crystal seed type by introducing the competition mechanism of strong reductant/strong oxidizer
Choosing, and by the stringent control size of continuous growth, pattern, realize the small size silver nanoparticle plate of 100% yield, with " gap " and
The large scale silver nanoparticle plate of " hot spot ", ultra-thin, super large draw ratio (1000:1) large scale silver nanoparticle plate and various monodisperses
Nucleocapsid silver nanoparticle plate.The above product has in fields such as printed electronic, thin-film device and nanometer waveguides widely answers
Use foreground.
Technical solution：The synthetic method of the ultra-thin silver nanoparticle plate of the present invention includes the following steps：
Step 1：Crystal seed is grown and screening
Silver nitrate and surfactant are mixed, stirs 1-3 minutes, is configured to mixed solution a, the wherein concentration of silver ion
For 0.1-100mmol/L；Excessive hydrogen peroxide solution is added into mixed solution a, is sufficiently stirred, wherein hydrogen peroxide is in reactant
A concentration of 0.5-1000mmol/L in system is 5 times of silver nitrate concentration or more；After stirring evenly, excessive strong reduction is added
Agent；At this point, growth-etching process that the galactic longitude in solution is gone through repeatedly, taken turns more, along with solution colour after：It is transparent, black, light
A series of yellow, black, yellow, black variations finally obtain the twin seed-solution of crystal seed type highly consistentization；
Step 2：It is prepared by the controllable monodisperse silver nanoparticle plate of size
The seed-solution that step 1 obtains is taken, 10-1000 times of deionized water dilution is added, and reducing agent is added thereto
And surfactant, obtain mixed solution b；Silver nitrate solution is added into mixed solution b, is used for the growth of silver nanoparticle plate,
A concentration of 0.01-100mmol/L of middle silver ion in the reaction system；With the increase of silver nitrate concentration in reaction system, silver
Nano-plates are gradually grown up, mixed solution after：A series of color changes such as Huang, orange, plum, purple, indigo plant, ultimately generate 100% production
The first silver nanoparticle plate solution of rate, size are accurate adjustable at 10-2000 nanometers；
Step 3：Silver nanoparticle plate with random " gap " and " hot spot " is taken turns continuous growth more and is prepared
The first the silver nanoparticle plate solution obtained on a small quantity by step 2, addition deionized water is taken to be diluted to silver-colored elemental concentration and be
0.001-100mmol/L；A small amount of hydrogen peroxide solution is added thereto, is sufficiently stirred 3-5 minutes, carries out pre-etching, it is stringent to control
A concentration of 0.001-100mmol/L of hydrogen peroxide in system keeps nano-plates edge roughening while being unlikely to broken or decomposing；In advance
Etching terminates that surfactant and reducing agent is added thereto successively again, is uniformly mixing to obtain mixed solution c；To mixed solution c
Middle addition silver nitrate solution, silver nitrate can generate hydrogen ion while reduction, and often wheel silver ion is in the reaction system for control
A concentration of 0.01-100mmol/L etches the coarse site in edge, the repair process phase of this etching process and the hydrogen atom of reduction
Mutually competition ensures to be unlikely to broken while edge forms cracking or decompose；Fully after reaction, deionized water is added and is diluted to silver
Elemental concentration is 0.001-100mmol/L；The 5-6 that repeats the above steps takes turns, and solution colour gradually bleaches, and the distinguishable silver of naked eyes occurs
White particles are suspended in solution, and forming edge cracking band, there are many second of silver nanoparticle plates in random " gap " and " hot spot "
Solution, when take turns number increase to 8 wheels it is above when, the sizes of nano-plates reaches 3-10 micron, and increases with wheel number, and size is kept dynamically
Stablize, the yield of second of silver nanoparticle plate can be improved by continuing growing wheel number；
Step 4：The preparation of edge smooth superelevation draw ratio, super large and ultra-thin silver nanoparticle plate
The first the silver nanoparticle plate solution obtained on a small quantity by step 2, addition deionized water is taken to be diluted to silver-colored elemental concentration and be
0.01-100mmol/L；Hydrogen peroxide solution and alkali halide are added thereto, accurately controls the concentration of hydrogen peroxide in system
For 0.001-100mmol/L, a concentration of 0.001-100mmol/L of alkali halide, to the nanometer in entire reaction process
Plate pattern is screened in real time, and the nano-plates for keeping edge coarse are decomposed rapidly, only retains the good nano-plates of crystal orientation for continuous life
It is long；Surfactant and reducing agent is added thereto again, stirs 1-3 minutes, obtains mixed solution d；It is added into mixed solution d
Silver nitrate solution, a concentration of 0.01-100mmol/L of silver ion in the reaction system；Fully after reaction, it is added 10-100 times
Deionized water dilutes；Within the 2-3 that repeats the above steps wheels, the silver nanoparticle plate growth limit can be broken through, obtains diameter on 20 microns of left sides
The right side, and thickness is less than 20 nanometers, draw ratio is up to 1000：The smooth superelevation draw ratio in 1 edge, super large and ultra-thin the third are received
Rice plate solution；
Step 5：It is prepared by nucleocapsid silver nanoparticle plate
It is that raw material prepares nucleocapsid using the silver nanoparticle plate solution obtained by step 2 or step 3 or step 4 preparation process
Nano-plates heterojunction structure, the specific method is as follows：
Ethyl orthosilicate TEOS is dissolved in ethyl alcohol, the precursor solution that volume fraction is 0.1%-10%, note are configured to
Make solution A；The silver nanoparticle plate solution centrifugation made from step 2 or step 3 or step 4 in right amount is taken, dilutes and quality point is added
Number is the hydrogen peroxide solution of 10%-30%, is configured to solution B；By 1：The ratio of (0.01-10) mixes solution A, B, persistently stirs
It mixes 5 hours or more；By centrifuging the unreacted excessive drug of removal, obtains uniform, monodispersed core-shell structural ultra-thin silver and receive
Rice plate.
The surfactant includes：Polyvinylpyrrolidone PVP, trisodium citrate, mercaptan, polymethylacrylic acid, benzene
Formic acid or sodium lactate；A concentration of 0.01-1000mmol/L of surfactant in the reaction system, in reaction system silver nitrate with
The molar ratio of surfactant is 1:(0.1-10).
The strong reductant includes：Ascorbic acid AA, formaldehyde, hydrazine hydrate or sodium borohydride；It is strong also in the reaction system
A concentration of 0.5-1000mmol/L of former agent is 5 times of silver nitrate concentration or more.
The reducing agent includes：Ascorbic acid, formaldehyde, hydrazine hydrate or polyalcohol；Reducing agent in the reaction system dense
Degree is 0.01-100mmol/L.
The surfactant includes：Polyvinylpyrrolidone, trisodium citrate, mercaptan, polymethylacrylic acid, grape
Sodium saccharate or lauryl sodium sulfate SDS；A concentration of 0.01-100mmol/L of surfactant in the reaction system.
The surfactant includes：Polymethylacrylic acid, sodium gluconate, trisodium citrate, mercaptan or polyethylene
Pyrrolidones；A concentration of 0.001-100mmol/L of surfactant in the reaction system.
The reducing agent includes：Ascorbic acid, formaldehyde, hydrazine hydrate or polyalcohol；Reducing agent in the reaction system dense
Degree is 0.001-100mmol/L.
The alkali halide is：Sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide or potassium iodide；Wherein, alkali
A concentration of 0.001-100mmol/L of metal halide in the reaction system.
The surfactant includes：Polymethylacrylic acid, sodium gluconate, trisodium citrate, mercaptan or polyethylene
Pyrrolidones；A concentration of 0.001-100mmol/L of surfactant in the reaction system.
The reducing agent includes：Ascorbic acid, formaldehyde, hydrazine hydrate or polyalcohol；Reducing agent in the reaction system dense
Degree is 0.001-100mmol/L.
In four the method for the present invention the step of, hydrogen peroxide solution and alkali halide provide, and there is superpower oxide etch to make
Oxonium ion/halide ion etching agent screens the nano-plates pattern in entire reaction process, keeps edge thick in real time
Rough nano-plates are decomposed rapidly, only retain the good nano-plates of crystal orientation for continuous growth.But hydrogen peroxide in system need to be accurately controlled
A concentration of 0.001-100mmol/L, a concentration of 0.001-100mmol/L of alkali halide is to ensure radial good nanometer
Plate is not broken off.Simultaneously as silver nitrate can generate hydrogen ion while reduction, as wheel number increases, hydrogen ion is gradual
Accumulation, oxide etch effect are more and more obvious, therefore to obtain super large, ultra-thin silver nanoparticle plate, it is necessary to reduce reaction to the greatest extent
Number is taken turns, hydrionic accumulation is inhibited.
Advantageous effect：The present invention has the following advantages that compared with prior art：
1. the present invention proposes a kind of novel crystal seed preparation method, compared with previously reported method, this method exists
Have in terms of screening crystal seed method significant advanced.Oxidation/reduction by introducing strong reductant and strong oxidizer competes machine
System screens crystal seed type, has etched away isotropism crystal seed, realized the preparation of the plane twin crystal seed of highly consistentization, from
Source inhibits the generation of non-nano plate particle, is the breakthrough to existing nano-plates preparation method.Based on crystalline substance proposed by the present invention
Kind preparation method, realizes magnanimity under room temperature, water base environment, high concentration, monodisperse silver nanoparticle plate (the first of 100% yield
Silver nanoparticle plate) preparation.
2. monodisperse silver nanoparticle plate solution proposed by the present invention, absorption peak are unimodal in visible-range, halfwidth is most
Low is only 80 nanometers, is the one third of the prior art.In same volume aqueous solution, yield is 100 times of the prior art.And it closes
It is easy to operate at method, success rate is high, pollution-free, sample size can accuracy controlling, preparation process be not necessarily to complex device, it can be achieved that
High-volume quickly production, is particularly suitable for industrialization.
3. present invention firstly provides a kind of systems of the completely new silver nanoparticle harden structure with random " gap " and " hot spot "
Preparation Method (second of nano-plates), what this structure had not been reported before." gap " and " hot spot " size of these random distributions
Minimum is only several nanometers, is distributed Relatively centralized, it is easy to encourage " gap pattern " so that local electric field intensity is obtained on hundred
Thousand times of enhancing.Meanwhile this macro-size has apparent two dimensional conductive pattern in 5 microns or more of silver nanoparticle plate, can use
In the remote sensing Raman detection and high-definition remote sensing imaging technique of heterodoxy excitation/output.
4. the present invention realizes a kind of superelevation draw ratio, large scale, ultra-thin, monocrystal silver nano-plates preparation (third for the first time
Kind nano-plates).This ultra-thin silver nanoparticle board size is in 20 microns, and thickness is at 20 nanometers hereinafter, draw ratio is about 1000:1,
It is 5-10 times of existing report.Its surface etc. from exciton member resonance peak (SPR) can red shift to mid and far infrared, even THz wave
Section, the blank of surface plasmons nano-plates material can be used by having filled up these wave bands.It can also be by electron beam lithography system
The standby two-dimensional waveguide device at high quality is applied to the device exploitation in the fields such as optic communication, quantum optices.
Description of the drawings
Fig. 1 is scanning electron microscope (SEM) figure of monodisperse silver nanoparticle plate in embodiment 1.
Fig. 2 is the scanning electron microscope diagram of the silver nanoparticle plate with random " gap " and " hot spot " in embodiment 2, wherein
Interior illustration is transmission electron microscope (TEM) image in region at edge " gap " and " hot spot ".
Fig. 3 is the superelevation draw ratio that edge is smooth in embodiment 3, the scanning electron microscope of super large and ultra-thin silver nanoparticle plate
Figure.
Specific implementation mode
It is further illustrated the present invention below by specific embodiment and comparative example：
Embodiment 1
Step 1：Crystal seed is grown and screening
10mL deionized waters are taken, silver nitrate solution and the 200 μ L that 100 a concentration of 0.5mol/L of μ L are added thereto successively are dense
Degree is the polyvinylpyrrolidonesolution solution of 3mol/L, stirs 3 minutes, is configured to mixed solution a；It is added 500 into mixed solution a
The hydrogen peroxide solution of a concentration of 1mol/L of μ L, is sufficiently stirred；The hydration of 500 a concentration of 1mol/L of μ L is added after stirring
Hydrazine solution；At this point, growth-etching process that the galactic longitude in solution is gone through repeatedly, taken turns more, along with solution colour after：Transparent,
A series of black, yellowish, black, yellow, black variations finally obtain the twin seed-solution of crystal seed type highly consistentization；
Step 2：It is prepared by the controllable monodisperse silver nanoparticle plate of size
1L deionized waters are taken, the seed-solution obtained in 5mL step 1, a concentration of 1mol/L of 5mL is added thereto successively
Polyvinylpyrrolidonesolution solution and a concentration of 1mol/L of 6mL ascorbic acid solution, obtain mixed solution b；After being sufficiently stirred,
The silver nitrate solution of a concentration of 0.1mol/L of 100mL is added into mixed solution b；As reaction carries out, silver nanoparticle plate is gradually grown
Greatly, mixed solution after：A series of color changes such as Huang, orange, plum, purple, indigo plant ultimately generate the first silver of 100% yield
Nano-plates solution.
The scanning electron microscope diagram of the first silver nanoparticle plate obtained is shown in Fig. 1, as shown in Figure 1, silver prepared by embodiment 1
Nano-plates are evenly distributed, without other patterns, a diameter of 400 ran, and pattern, size uniformity.
Embodiment 2
Step 1：Crystal seed is grown and screening
5mL deionized waters are taken, silver nitrate solution and the 60 μ L that 60 a concentration of 1mol/L of μ L are added thereto successively are a concentration of
The sodium dodecyl sulfate solution of 2mol/L stirs 1 minute, is configured to mixed solution a；It is dense that 300 μ L are added into mixed solution a
Degree is the hydrogen peroxide solution of 1mol/L, is sufficiently stirred；The sodium borohydride of 500 a concentration of 1mol/L of μ L is added after stirring
Solution；At this point, growth-etching process that the galactic longitude in solution is gone through repeatedly, taken turns more, along with solution colour after：Transparent, black,
A series of yellowish, black, yellow, black variations finally obtain the twin seed-solution of crystal seed type highly consistentization；
Step 2：It is prepared by the controllable monodisperse silver nanoparticle plate of size
60mL deionized waters are taken, the seed-solution obtained in 400 μ L step 1 is added thereto successively, 50 μ L are a concentration of
The citric acid solution of the sodium dodecyl sulfate solution of 1mol/L and 100 a concentration of 1mol/L of μ L, obtains mixed solution b；Fully
After stirring, the silver nitrate solution of a concentration of 0.5mol/L of 1.5mL is added into mixed solution b；As reaction carries out, silver nanoparticle plate
Gradually grow up, mixed solution after：A series of color changes such as Huang, orange, plum, purple, indigo plant ultimately generate the of 100% yield
A kind of silver nanoparticle plate solution.
Step 3：Silver nanoparticle plate with random " gap " and " hot spot " is taken turns continuous growth more and is prepared
60mL deionized waters are taken, the silver nanoparticle plate solution that 200 μ L steps 5 obtain is added thereto；50 μ L are added thereto
The hydrogen peroxide solution of a concentration of 0.5mol/L is sufficiently stirred 5 minutes, carries out pre-etching；Pre-etching terminates successively thereto to add again
Enter the citric acid solution of the sodium dodecyl sulfate solution and 100 a concentration of 1mol/L of μ L of 50 a concentration of 1mol/L of μ L, stirring is equal
It is even to obtain mixed solution c；The silver nitrate solution of a concentration of 0.5mol/L of 1.5mL is added into mixed solution c；Fully reaction
Afterwards, 10mL solution is taken, it is 60ml to add deionized water to be diluted to volume；It repeats above-mentioned steps 8 in step 3 to take turns, solution colour is gradual
Bleach, the distinguishable silvery white little particle of naked eyes occur and be suspended in solution, formed edge cracking band there are many random " gap " and
Second of the silver nanoparticle plate solution of " hot spot ".
The scanning electron microscope diagram of second of silver nanoparticle plate obtained is shown in Fig. 2, as shown in Figure 2, silver prepared by embodiment 2
There are many random " gap " and " hot spot ", a diameter of 7 microns for nano-plates band.
Embodiment 3
Step 1：Crystal seed is grown and screening
8mL deionized waters are taken, silver nitrate solution and the 100 μ L that 60 a concentration of 1mol/L of μ L are added thereto successively are a concentration of
The polymethyl acid solution of 1mol/L stirs 2 minutes, is configured to mixed solution a；100 μ L concentration are added into mixed solution a
For the hydrogen peroxide solution of 2mol/L, it is sufficiently stirred；The citric acid that 100 a concentration of 3mol/L of μ L are added after stirring is molten
Liquid；At this point, growth-etching process that the galactic longitude in solution is gone through repeatedly, taken turns more, along with solution colour after：It is transparent, black, light
A series of yellow, black, yellow, black variations finally obtain the twin seed-solution of crystal seed type highly consistentization；
Step 2：It is prepared by the controllable monodisperse silver nanoparticle plate of size
80mL deionized waters are taken, the seed-solution obtained in 400 μ L step 1 is added thereto successively, 50 μ L are a concentration of
The formalin of the polymethyl acid solution of 1mol/L and 100 a concentration of 1mol/L of μ L, obtains mixed solution b；It is sufficiently stirred
Afterwards, the silver nitrate solution of a concentration of 0.6mol/L of 2mL is added thereto；As reaction carries out, silver nanoparticle plate is gradually grown up, and is mixed
Solution after：A series of color changes such as Huang, orange, plum, purple, indigo plant, the first the silver nanoparticle plate for ultimately generating 100% yield are molten
Liquid.
Step 3：The preparation of edge smooth superelevation draw ratio, super large and ultra-thin silver nanoparticle plate
80mL deionized waters are taken, sequentially add the silver nanoparticle plate solution that 100 μ L steps 5 obtain thereto, 100 μ L are a concentration of
The hydrogen peroxide solution of the potassium bromide solution of 0.01mol/L and 500 a concentration of 0.2mol/L of μ L；It is a concentration of that 50 μ L are added thereto again
The formalin of the polymethyl acid solution of 1mol/L and 100 a concentration of 1mol/L of μ L stirs 3 minutes, obtains mixed solution
d；The silver nitrate solution of a concentration of 0.6mol/L of 2mL is added into mixed solution d；Fully reaction after, take 10mL solution, add from
It is 80ml that sub- water, which is diluted to volume,；Within above-mentioned steps 2 are taken turns in repetition step 3, the silver nanoparticle plate growth limit can be broken through, is obtained
Diameter is in 20 microns, and thickness is less than 20 nanometers, and draw ratio is up to 1000：The smooth superelevation draw ratio in 1 edge, super large and
The third ultra-thin nano-plates solution.
The scanning electron microscope diagram of the third silver nanoparticle plate obtained is shown in Fig. 3, from the figure 3, it may be seen that silver prepared by embodiment 3
Nano-plates flush edge, size is big, and diameter is in 20 microns, and thickness is at 20 nanometers hereinafter, draw ratio is about 1000:1.
In addition, those skilled in the art can also make other variations in spirit of that invention, these are smart according to the present invention certainly
Change made by god, should all be included in scope of the present invention.
Claims (8)
1. a kind of synthetic method of ultra-thin silver nanoparticle plate, it is characterised in that the synthetic method includes the following steps：
Step 1：Crystal seed is grown and screening
Silver nitrate and surfactant are mixed, stirs 1-3 minutes, is configured to mixed solution a, wherein silver ion is a concentration of
0.1-100mmol/L；Excessive hydrogen peroxide solution is added into mixed solution a, is sufficiently stirred, wherein hydrogen peroxide is in reaction system
In a concentration of 0.5-1000mmol/L, be 5 times of silver nitrate concentration or more；After stirring evenly, excessive strong reductant is added；
At this point, growth-etching process that the galactic longitude in solution is gone through repeatedly, taken turns more, along with solution colour after：Transparent, black, yellowish,
A series of black, yellow, black variations finally obtain the twin seed-solution of crystal seed type highly consistentization；
Step 2：It is prepared by the controllable monodisperse silver nanoparticle plate of size
The seed-solution that step 1 obtains is taken, 10-1000 times of the deionized water that taken seed-solution volume is added dilutes, and to
Reducing agent and surfactant is wherein added, obtains mixed solution b；Silver nitrate solution is added into mixed solution b, is received for silver
The growth of rice plate, the wherein a concentration of 0.01-100mmol/L of silver ion in the reaction system；With silver nitrate in reaction system
The increase of concentration, silver nanoparticle plate are gradually grown up, mixed solution after：Huang, orange, plum, purple, a series of blue color changes, finally
The first silver nanoparticle plate solution of 100% yield is generated, the nano-plates size dimension of synthesis is accurate adjustable at 10-2000 nanometers；
Step 3：Silver nanoparticle plate with random " gap " and " hot spot " is taken turns continuous growth more and is prepared
The first the silver nanoparticle plate solution obtained on a small quantity by step 2, addition deionized water is taken to be diluted to silver-colored elemental concentration and be
0.001-100mmol/L；A small amount of hydrogen peroxide solution is added thereto, is sufficiently stirred 3-5 minutes, carries out pre-etching, it is stringent to control
A concentration of 0.001-100mmol/L of hydrogen peroxide in system keeps nano-plates edge roughening while being unlikely to broken or decomposing；In advance
Etching terminates that surfactant and reducing agent is added thereto successively again, is uniformly mixing to obtain mixed solution c；To mixed solution c
Middle addition silver nitrate solution, silver nitrate can generate hydrogen ion while reduction, and often wheel silver ion is in the reaction system for control
A concentration of 0.01-100mmol/L etches the coarse site in edge, the repair process phase of this etching process and the hydrogen atom of reduction
Mutually competition ensures to be unlikely to broken while edge forms cracking or decompose；Fully after reaction, deionized water is added and is diluted to silver
Elemental concentration is 0.001-100mmol/L；Step 3 above-mentioned steps 5-6 wheels are repeated, solution colour gradually bleaches, and naked eyes occur can
The silvery white little particle distinguished is suspended in solution, and forming edge cracking band, there are many second of the silver medals in random " gap " and " hot spot "
Nano-plates solution, when take turns number increase to 8 wheels it is above when, the size dimensions of nano-plates reaches 3-10 micron, and with wheel number growth, ruler
The yield of second of silver nanoparticle plate can be improved by continuing growing wheel number for very little holding dynamic stability；
Step 4：The preparation of edge smooth superelevation draw ratio, super large and ultra-thin silver nanoparticle plate
The first the silver nanoparticle plate solution obtained on a small quantity by step 2, addition deionized water is taken to be diluted to silver-colored elemental concentration and be
0.01-100mmol/L；Hydrogen peroxide solution and alkali halide are added thereto, accurately controls the concentration of hydrogen peroxide in system
For 0.001-100mmol/L, a concentration of 0.001-100mmol/L of alkali halide, to the nanometer in entire reaction process
Plate pattern is screened in real time, and the nano-plates for keeping edge coarse are decomposed rapidly, only retains the good nano-plates of crystal orientation for continuous life
It is long；Surfactant and reducing agent is added thereto again, stirs 1-3 minutes, obtains mixed solution d；It is added into mixed solution d
Silver nitrate solution, a concentration of 0.01-100mmol/L of silver ion in the reaction system；Fully after reaction, it is added 10-100 times
Deionized water dilutes；It repeats within step 4 above-mentioned steps 2-3 wheels, the silver nanoparticle plate growth limit can be broken through, obtain diameter 20
Microns, and thickness is less than 20 nanometers, draw ratio is up to 1000：The smooth superelevation draw ratio in 1 edge, super large and ultra-thin
Three kinds of nano-plates solution；
Step 5：It is prepared by nucleocapsid silver nanoparticle plate
It is that raw material prepares core-shell nano using the silver nanoparticle plate solution obtained by step 2 or step 3 or step 4 preparation process
Plate heterojunction structure, the specific method is as follows：
Ethyl orthosilicate TEOS is dissolved in ethyl alcohol, the precursor solution that volume fraction is 0.1%-10% is configured to, is denoted as molten
Liquid A；The silver nanoparticle plate solution centrifugation made from step 2 or step 3 or step 4 in right amount is taken, dilutes and mass fraction is added and is
The hydrogen peroxide solution of 10%-30%, is configured to solution B；By 1：The ratio of (0.01-10) mixes solution A, B, persistently stirs 5
Hour or more；By centrifuging the unreacted excessive drug of removal, uniform, monodispersed core-shell structural ultra-thin silver nanoparticle is obtained
Plate.
2. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The surfactant includes：
Polyvinylpyrrolidone PVP, trisodium citrate, mercaptan, polymethylacrylic acid, benzoic acid or sodium lactate；Surfactant is anti-
Answer a concentration of 0.01-1000mmol/L in system, the molar ratio of silver nitrate and surfactant is 1 in reaction system:(0.1-
10)。
3. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The strong reductant includes：
Ascorbic acid AA, formaldehyde, hydrazine hydrate or sodium borohydride；A concentration of 0.5-1000mmol/L of strong reductant in the reaction system,
It is 5 times or more of silver nitrate concentration.
4. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The reducing agent includes：It is anti-
Bad hematic acid, formaldehyde, hydrazine hydrate or polyalcohol；A concentration of 0.01-100mmol/L of reducing agent in the reaction system.
5. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The surfactant packet
It includes：Polyvinylpyrrolidone, trisodium citrate, mercaptan, polymethylacrylic acid, sodium gluconate or lauryl sodium sulfate SDS；
A concentration of 0.01-100mmol/L of surfactant in the reaction system.
6. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The surfactant packet
It includes：Polymethylacrylic acid, sodium gluconate, trisodium citrate, mercaptan or polyvinylpyrrolidone；Surfactant is in reactant
A concentration of 0.001-100mmol/L in system.
7. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The reducing agent includes：It is anti-
Bad hematic acid, formaldehyde, hydrazine hydrate or polyalcohol；A concentration of 0.001-100mmol/L of reducing agent in the reaction system.
8. the synthetic method of ultra-thin silver nanoparticle plate as described in claim 1, it is characterised in that：The alkali halide is：
Sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide or potassium iodide；Wherein, alkali halide in the reaction system dense
Degree is 0.001-100mmol/L.
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