CN107297511A - The method that dynamic reversible regulates and controls surface plasma body resonant vibration property - Google Patents
The method that dynamic reversible regulates and controls surface plasma body resonant vibration property Download PDFInfo
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Abstract
The invention discloses a kind of method that dynamic reversible regulates and controls surface plasma body resonant vibration property, it includes:Chalcogen copper compound coats the preparation of noble metal nanometer material;Regulation and control to the surface plasma resonance property of the nano material;And the step such as reversible regulation and control of surface plasma resonance property to the nano material.The present invention realizes the adjustability of surface plasma body resonant vibration property by controlled material size, pattern and carrier concentration, and technique is simple, condition is easily-controllable, can be repeated several times, for realizing the design of optics, control and switch significant, also have potential application in detection, infrared switch and infrared sensor.
Description
Technical field
The invention belongs to surface phasmon photonics, and in particular to a kind of dynamic reversible regulates and controls surface plasma body resonant vibration
The method of property, i.e., realize surface plasma body resonant vibration property by the pattern of controlled material, size and carrier concentration
Adjustability.
Background technology
Local surface plasmon resonance (LSPR) is more common in the free electron in noble metal nano particles under additional electromagnetic field
Generation coherent oscillation, so that the enhanced phenomenon of absorption and scattering resonance produced.LSPR is in the regulation and control of nanoscale optics
Strong means, can break through optical diffraction limit.A series of research directions are expedited the emergence of around this unique optical phenomena, for example
Surface-enhanced Raman, surface-enhanced fluorescence, surface plasma photocatalysis based on LSPR surfaces optical electric field enhancement effect etc.,
It is set to obtain extensive concern in the field such as Single Molecule Detection, optical imagery and treatment, photovoltaic;In addition, LSPR characteristics are also
There is splendid application prospect in fields such as surface plasma waveguide, photoswitch, Meta Materials design and electro-optical modulations.
At present, the material with adjustable surface plasma body resonant vibration property mainly has two classes:One is metal nano material, two
It is doped semiconductor nanocrystal material.For metal nanoparticle, its surface plasma body resonant vibration property is strongly dependent upon chemistry
Composition, the dielectric constant of surrounding environment, granule-morphology, but the size of particle is depended on to lesser extent.Most of gold
The surface plasma body resonant vibration property of metal nanometer material is just determined substantially in synthesis, and subsequent treatment is difficult to be adjusted again.
Its optical property is limited primarily to visual field and ultra-violet (UV) band, and only a small number of metal nano materials is such as Au, Ag, Cu and Pt
Absorption can involve infrared region, and there is the metal nano material of infrared response there was only the various of Au correlations for systematic research
Nanostructured.But the carrier concentration of precious metal material is fixed, near-field coupling is also more to be drawn by the machinery of place substrate
The method such as stretch to realize, it is more difficult to realize dynamic, the active control of reversible nanocomposite optical property.On the other hand, for semiconductor
Nano material, when particle size is less than bohr exciton radii, its surface plasma body resonant vibration property can be adjusted by particle diameter
Section;And because carrier concentration is controllable in certain limit, the optical absorption ranges of doped semiconductor nanocrystal material can cover from
Visual field arrives infrared region whole region to ultra-violet (UV) band again.Therefore, how pattern by semiconductor nano material, chemical constituent
Regulate and control the energy and intensity of surface plasmon resonance with free carrier concentration, and utilize the knot in nano composite material
The structure of structure and surface and interface is acted on to obtain reversible near-field coupling, is the key for realizing nanocomposite optical active control, and it is realized
Design for optics, control and switch significant, also have in detection, infrared switch and infrared sensor
Potential application.
Chalcogen copper compound nano material, as a kind of new surface plasma body resonant vibration material, its special optical property into
For research contents important in recent years.The change of its granular size, pattern and carrier concentration caused by copper defect level, be
The surface plasma body resonant vibration property of controllable adjustment nano material provides theoretical foundation.
Regulation process complexity is there is in the method for regulation and control nano-material surface plasma resonance property at present, cost is too high,
Efficiency is low, the problems such as repeatability is poor.In consideration of it, overcome defect present in prior art there is provided it is a kind of it is simple, economical,
The method for the regulation and control surface plasma body resonant vibration property that controllable, effect is good, can be iteratively repeated is that the art is urgently to be resolved hurrily
Problem.
The content of the invention
For the problems of the prior art, it is a primary object of the present invention to provide a kind of dynamic reversible regulation and control surface plasma
The method for the property that resonates, to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of method of dynamic reversible regulation and control surface plasma body resonant vibration property provided in an embodiment of the present invention comprises the following steps:
(1) nano material that dispersed chalcogen copper compound coats noble metal, the nanometer are prepared in protective atmosphere
Material includes the chalcogen copper compound of noble metal nano particles and the cladding noble metal nano particles;
(2) the nano material exposure prepared step (1) in atmosphere, and monitors the surface plasma of the nano material
Resonant absorption wavelengths, realize the regulation and control to the surface plasma resonance property of the nano material;
(3) when the nano material by atmosphere be exposed to surface plasmon resonance absorption wavelength it is constant when, received to described
Cuprous ion solution is added in rice material, and after cuprous ion solution is added every time, monitors surface of the nano material etc.
Ion resonance absorbing wavelength, realizes the reversible regulation and control to the surface plasma resonance property of the nano material;
(4) cuprous ion in the nano material after being handled through step (3) is removed, and again by the nano material
Exposure in atmosphere, while monitoring the surface plasmon resonance absorption wavelength of the nano material, is realized to the nano material
Surface plasma resonance property reversible regulation and control.
Among some embodiments, the method for the dynamic reversible regulation and control surface plasma body resonant vibration property includes:Repeat to walk
Suddenly the operation of (2)~step (4) more than twice, to reach to the progress of the surface plasma resonance property of the nano material
The purpose of reversible regulation and control.
The embodiment of the present invention additionally provides a kind of method based on local surface plasma resonance nature examination reducing agent, and it is wrapped
Include:
Testing sample and metal chalcogenides nano material and/or metal chalcogenides are coated to the nano material of noble metal
Be sufficiently mixed in liquid-phase system, and monitor in real time in Visible-to-Near InfaRed area the metal chalcogenides nano material and/or
The change of the surface plasmon absorption wavelength of the nano material of metal chalcogenides cladding noble metal, when the metal
The absworption peak that chalcogen compound nano material and/or the nano material of metal chalcogenides cladding noble metal are in long wavelength is red
Move, and when absorption intensity reduction, then judge to contain reducing agent in the testing sample.The liquid-phase system includes the aqueous solution,
And/or, the metal chalcogenides include metal selenide or metal sulfide, but not limited to this.
Compared with prior art, advantages of the present invention includes:
(1) the invention provides a kind of method that dynamic reversible regulates and controls surface plasma body resonant vibration property, by being received to above-mentioned
The surface plasma body resonant vibration property of rice material is regulated and controled, so as to monitor its optical absorption curve with Cu in measure solution+、
The change of the reducing agent addition amounts such as VC, and then can realize to Cu in solution+, VC etc. optical detection, this method is not
It is only simple to operate, and with higher sensitivity.
(2) a kind of dynamic reversible that the present invention is provided regulates and controls the method for surface plasma body resonant vibration property, and surface etc. can be achieved
The reversible controllable adjustment of gas ions resonance property, absorption spectrum can carry out broadband regulation from visible region to infrared light district, adjust
Control process is simple to operation, controllability is strong, effect is good, can be repeated several times, in device design, control, switch and sensing etc.
Aspect has extraordinary application prospect.
Brief description of the drawings
Fig. 1 is a kind of technological process of dynamic reversible regulation and control surface plasma body resonant vibration property in a typical embodiments of the invention
Figure;
Fig. 2 is that the one kind provided in the embodiment of the present invention 1 is coated under polyacrylic acid surfactant in bar-shaped gold nano grain
The transmission electron microscope picture of copper selenide composite nano materials;
Fig. 3 is one kind gold bar-shaped under PDDA surfactant provided in the embodiment of the present invention 6
The transmission electron microscope picture of copper selenide composite nano materials is coated on nano particle;
Fig. 4 is that the one kind provided in the embodiment of the present invention 2 is coated under polyacrylic acid surfactant in bar-shaped gold nano grain
Copper selenide composite nano materials are with air exposure time increased ultraviolet-infrared vis spectroscopy spectrogram;
Fig. 5 is one kind gold bar-shaped under PDDA surfactant provided in the embodiment of the present invention 7
Copper selenide composite nano materials are coated on nano particle with air exposure time increased ultraviolet-infrared vis spectroscopy spectrogram;
Fig. 6 is that the one kind provided in the embodiment of the present invention 3 is coated under polyacrylic acid surfactant in bar-shaped gold nano grain
Ultraviolet-infrared vis spectroscopy spectrogram that copper selenide composite nano materials change with the addition of cuprous ion solution;
Fig. 7 is one kind gold bar-shaped under PDDA surfactant provided in the embodiment of the present invention 8
Ultraviolet-infrared vis spectroscopy that copper selenide composite nano materials change with the addition of cuprous ion solution is coated on nano particle
Spectrogram;
Fig. 8 is that the one kind provided in the embodiment of the present invention 4 is coated under polyacrylic acid surfactant in bar-shaped gold nano grain
Copper selenide composite nano materials are removed after cuprous ion, with increased ultraviolet-infrared vis spectroscopy spectrum of air exposure time
Figure;
Fig. 9 is one kind gold bar-shaped under PDDA surfactant provided in the embodiment of the present invention 9
Copper selenide composite nano materials are coated on nano particle to remove after cuprous ion, it is ultraviolet-infrared with the increase of air exposure time
Vis spectroscopy spectrogram;
Figure 10 is that provide in the embodiment of the present invention 5 a kind of coats copper selenide in the bar-shaped gold nano grain of different draw ratios
The transmission electron microscope picture of composite nano materials;
Figure 11 is that provide in the embodiment of the present invention 5 a kind of coats copper selenide in the bar-shaped gold nano grain of different draw ratios
Ultraviolet-infrared vis spectroscopy spectrogram of composite nano materials;
Figure 12 is a kind of copper selenide nanometer synthesized under polyacrylic acid surfactant provided in the embodiment of the present invention 12
During grain detection reducing agent cuprous ion, the variation diagram of its surface plasmon resonance absorption spectrum, curve a in figure, b, c, d,
It is 0,7.76 × 10 that e, f, g represent the concentration of cuprous ion respectively-6mol/L、1.54×10-5mol/L、3.05×10-5mol/L、
4.52×10-5mol/L、8.72×10-5mol/L、1.39×10-4Curve during mol/L;
Figure 13 is that the one kind provided in the embodiment of the present invention 11 is wrapped under polyacrylic acid surfactant in bar-shaped gold nano grain
When covering copper selenide composite nano materials detection reducing agent cuprous ion, the variation diagram of its surface plasmon resonance absorption spectrum, figure
It is 0,1.54 × 10 that middle curve a, b, c, d, e, f, g represent the concentration of cuprous ion respectively-5mol/L、3.05×10-5mol/L、
7.35×10-5mol/L、1.39×10-4mol/L、2.5×10-4mol/L、4.81×10-4Curve during mol/L.
Embodiment
More detailed explanation will hereafter be made to technical scheme.It is understood, however, that in the scope of the invention
It is interior, can be mutual between above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment)
It is combined, so as to constitute new or preferred technical scheme.As space is limited, no longer tire out one by one herein and state.
The one side of the embodiment of the present invention provides a kind of method that dynamic reversible regulates and controls surface plasma body resonant vibration property, its
Comprise the following steps:
(1) nano material that dispersed chalcogen copper compound coats noble metal, the nanometer are prepared in protective atmosphere
Material includes the chalcogen copper compound of noble metal nano particles and the cladding noble metal nano particles;
(2) the nano material exposure prepared step (1) in atmosphere, and monitors the surface plasma of the nano material
Resonant absorption wavelengths, realize the regulation and control to the surface plasma resonance property of the nano material;
(3) when the nano material by atmosphere be exposed to surface plasmon resonance absorption wavelength it is constant when, received to described
Cuprous ion solution is added in rice material, and after cuprous ion solution is added every time, monitors surface of the nano material etc.
Ion resonance absorbing wavelength, realizes the reversible regulation and control to the surface plasma resonance property of the nano material;
(4) cuprous ion in the nano material after being handled through step (3) is removed, and again by the nano material
Exposure in atmosphere, while monitoring the surface plasmon resonance absorption wavelength of the nano material, is realized to the nano material
Surface plasma resonance property reversible regulation and control.
Among some embodiments, the method for the dynamic reversible regulation and control surface plasma body resonant vibration property includes:Repeat to walk
Suddenly the operation of (2)~step (4) more than twice, to reach to the progress of the surface plasma resonance property of the nano material
The purpose of reversible regulation and control.
Among some embodiments, the chalcogen copper compound includes copper selenide or copper sulfide, but not limited to this.
Among some embodiments, the material of the noble metal nano particles includes Au Ag Pt Pd, tin, cobalt and nickel
In any one or two or more combinations, but not limited to this.
Among some embodiments, the preparation method of the nano material of the chalcogen copper compound cladding noble metal includes:
In protective atmosphere, noble metal nano particles are scattered in deionized water, and add surfactant, formation is received
Rice grain dispersion;
Protective atmosphere is maintained, while adding selenium source and/or sulphur source into the nanoparticle dispersion, reduction is added afterwards
Agent, obtains the reaction system that noble metal nano particles intermediate is coated containing selenium and/or sulphur;
Copper source is added into the reaction system containing selenium and/or sulphur cladding noble metal nano particles intermediate to be reacted,
Form the nano material that the chalcogen copper compound coats noble metal.
Among some more specific embodiment, the dynamic reversible regulates and controls the method bag of surface plasma body resonant vibration property
Include:Precious metal salt is scattered in the solvent containing surfactant, and the mixture to be formed is reached fluidized state, then is added
Enter reducing agent, form the noble metal nano particles.
Among some more specifically embodiment, the dynamic reversible regulates and controls the method bag of surface plasma body resonant vibration property
Include:During the noble metal nano particles are prepared, by the regulation and control of different experiments parameter, noble metal nano is realized
The regulation and control of the particle size of grain.Wherein described experiment parameter includes reducing agent, the Ag for preparing noble metal nano particles+And seed
The addition of liquid etc., but not limited to this.
Among some embodiments, the method for the dynamic reversible regulation and control surface plasma body resonant vibration property includes:Preparing
During the nanoparticle dispersion, by changing the type of surfactant in nano material preparation process, realization pair
The regulation and control of the appearance of nano material.
Among some embodiments, the protective atmosphere can be formed mainly by argon gas and/or nitrogen, but not limited to this.
Among some embodiments, described selenium source includes selenium dioxide, sodium selenide or selenous acid, but not limited to this.
Among some embodiments, described sulphur source includes sulphur powder or lauryl mercaptan, but not limited to this.
Among some embodiments, described copper source includes copper sulphate, copper nitrate or copper chloride, but not limited to this.
Among some embodiments, the amount of the material of copper and the amount of the material of selenium element in the selenium source in copper source
The ratio between be 1:1~4:1.
Among some embodiments, the amount of the material of copper and the amount of the material of element sulphur in the sulphur source in copper source
The ratio between be 1:1~4:1.
Among some embodiments, the reducing agent includes any one in ascorbic acid, sodium citrate, boron hydracid sodium
Or two or more combinations, but not limited to this.
Among some embodiments, the surfactant includes nonionic surface active agent or ionic surfactant
Agent, the nonionic surface active agent includes polyvinyl alcohol or polyethylene glycol, and the ionic surfactant includes 12
Appointing in sodium alkyl benzene sulfonate, lauryl sodium sulfate, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride
The combinations for one or more of anticipating, but not limited to this.
Among some embodiments, the cuprous ion solution preferably is selected from the cuprous ion solution of ascorbic acid reduction, described
Ascorbic acid reduction cuprous ion solution preparation method be ascorbic acid and copper ion are mixed to be formed it is cuprous from
Son.
Among some embodiments, the method that the dynamic reversible regulates and controls surface plasma body resonant vibration property, including it is following suitable
The step of sequence:
(1) using the liquid phase synthesizing method of simple green, dispersed chalcogen copper compound bag is prepared in inert gas atmosphere
Cover the nano material of noble metal.
(2) increase the air exposure time of nano material in step (1), once absorbed every 30min during beginning
Spectral measurement, mid-term carries out an absorption spectrum measurement every 1h, and the later stage carries out an absorption spectrum measurement every 2h,
Complete the regulation and control of the surface plasma resonance property of material.
(3) when the surface plasmon resonance absorption wavelength of nano material in step (2) no longer changes, ascorbic acid is added
The cuprous ion solution of reduction often changes the addition of a cuprous ion solution, with regard to once being absorbed in nano material
Spectral measurement, completes the reversible regulation and control of the surface plasma resonance property of material.
(4) cuprous ion in removal step (3) in nano material, is then exposed in air, during with exposure
Between growth, carry out the measurement of absorption spectrum every 30min during beginning, mid-term carries out an absorption spectrum every 1h
Measurement, the later stage carries out an absorption spectrum measurement every 2h, completes the reversible regulation and control of the surface plasma resonance property of material.
Step (2), (3), (4) repeatedly iterative cycles can be carried out, and realize the repeatable of regulation and control surface plasma resonance property
Property.
(5) by adjusting noble metal granule size in nano material, and then the regulation and control to nano material size are realized, so that
Realize the adjustability of the surface plasma body resonant vibration property of material.Repeat step (2), (3), (4), can further controllable tune
Save the surface plasma resonance property of material.
(6) surfactant during nano material is prepared by change, the nano material for obtaining different-shape realizes it
The regulation and control of pattern, so as to realize the adjustability of the surface plasma body resonant vibration property of material.Repeat step (2), (3), (4),
The surface plasma resonance property of controllable adjustment material can further be realized.
The present invention proposes a kind of method based on local surface plasma resonance nature examination reducing agent, and it includes:
Testing sample and metal chalcogenides nano material and/or metal chalcogenides are coated to the nano material of noble metal
Be sufficiently mixed in liquid-phase system, and monitor in real time in Visible-to-Near InfaRed area the metal chalcogenides nano material and/or
The change of the surface plasmon absorption wavelength of the nano material of metal chalcogenides cladding noble metal, when the metal
The absworption peak that chalcogen compound nano material and/or the nano material of metal chalcogenides cladding noble metal are in long wavelength is red
Move, and when absorption intensity reduction, then judge to contain reducing agent in the testing sample.The liquid-phase system includes the aqueous solution,
And/or, the metal chalcogenides include metal selenide or metal sulfide, but not limited to this.
Among some embodiments, noble metal is coated by measuring the metal selenide nano material or metal selenide
The intensity of variation (change for absorbing peak position and intensity) of the absworption peak of the long wavelength of nano material, is realized to testing sample
The quantitative measurment of middle reduction agent content.
Among some embodiments, the reducing agent includes Cu+Or VC, but not limited to this.
The principle of the inventive method is:Testing sample (the particularly sample of solution shape) is added to metal selenide nanometer
In the nanomaterial solution of material or metal selenide cladding noble metal, its surface etc. is monitored in real time in visible-near infrared region
The change of gas ions resonant absorption wavelengths.When containing reducing agent in solution to be measured, nano material is in the absworption peak of long wavelength
Gradually red shift, absorption intensity is gradually reduced, and can quantitatively determine molten according to the intensity of variation of the absworption peak of nano material long wavelength
The content of reducing agent in liquid.
The method of dynamic reversible regulation and control surface plasma body resonant vibration property of the present invention can be widely used for the design of device, control
System, switch and sensing.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with drawings and Examples, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Not constituting conflict each other can just be mutually combined.
The present invention relates to a kind of method that dynamic reversible regulates and controls surface plasma body resonant vibration property, its mentality of designing is by regulation and control
Pattern, size and the carrier concentration of material, and then realize the reversible controllable adjustment of surface plasma body resonant vibration property.
Fig. 1, which is shown, realizes dynamic reversible regulation and control surface plasma body resonant vibration property in the typical embodiments of the present invention
Technological process, it is mainly included the following steps that:First, dispersed chalcogen copper compound cladding is prepared in inert gas
Noble metal nanometer material;Second, above-mentioned nano material implements dynamic in real time inhale in the presence of the increase air exposure time
Receive spectral measurement;3rd, the cuprous ion solution of ascorbic acid reduction is added in the nano material of previous step, with cuprous
The addition change of solion, synchronizes dynamic absorption spectrum measurement;4th, remove the Asia in above-mentioned nano material
Copper ion, again in air, carries out dynamic absorption spectrum in real time with the change of open-assembly time and measures;5th,
By regulating and controlling the granular size of noble metal in nano material and then realizing regulation and control to nano material size, repeat step two, three,
Four, while carrying out absorption spectrum measurement;Finally, change the surfactant in preparation process and then realize to nano material shape
The regulation and control of looks, repeat step two, three, four, while carrying out absorption spectrum measurement.
The present invention utilizes shirtsleeve operation mode, and novel mentality of designing is realized to the reversible of surface plasma body resonant vibration property
Regulation and control, condition is easy to control, effect is good, can be iteratively repeated, and is that the design, control and switch of the optics of specific wavelength are carried
New thinking is supplied.
The embodiment of the present invention 1 of embodiment 1 provides a kind of composite nano materials, prepares in accordance with the following steps:
(1) first, gold seeds solution is prepared.At room temperature by chlorauric acid solution and cetyl trimethylammonium bromide solution
Stir, rapidly join the reducing agent sodium borohydride solution of ice bath preservation, 2min is persistently stirred, then at 25~30 DEG C
Under the conditions of stand 30min to 1h obtain gold seeds solution.Secondly, golden rod growth-promoting media is prepared.At room temperature by hexadecane
The base trimethylammonium bromide aqueous solution, silver nitrate solution and chlorauric acid solution stir, and then add reducing agent ascorbic acid molten
Liquid, lasting stirring is until solution is in colourless.Finally, a certain amount of gold seeds solution prepared is added in golden rod growth-promoting media,
10s is stirred, 8~12h is then stood under the conditions of 25~35 DEG C obtains bar-shaped gold nano grain;
(2) bar-shaped gold nano grain obtained by step (1) is centrifuged, removes supernatant liquor, be re-dispersed into polyacrylic acid molten
In liquid, noble metal nano particles dispersion is formed;
(3) 10mmol selenium dioxide is added in dispersions, and ultrasonic disperse stirs 30min under inert gas shielding
30 DEG C are heated to, then 60mmol ascorbic acid is injected into dispersion, 10~20min is reacted, selenium is obtained and coats bar-shaped gold
The intermediate of nano particle;
(4) copper source mixed liquor is prepared:20mmol cupric sulfate pentahydrates and the mixing of 80mmol ascorbic acid.
(5) mixed liquor prepared by (4) is added into the solution containing intermediate obtained by step (3), protectiveness is maintained at
In atmosphere under 30 DEG C of heating stirrings, composite nano materials are obtained.
The present invention has carried out transmission electron microscope analysis to the gained composite nano materials of embodiment 1, as a result as shown in Fig. 2 can see
It is uniformly distributed to the composite nano materials in core shell structure.
The present invention of embodiment 2 is adjusted to the method for embodiment 1:Increase air open-assembly time in step (5), during beginning
An absorption spectrum measurement is carried out every 30min, mid-term carries out an absorption spectrum measurement every 1h, and the later stage is every 2h
An absorption spectrum measurement is carried out, as a result (arrow is shown in Fig. 4 gradually increases suction with the air exposure time as shown in Figure 4
Receive the variation tendency of spectrum), it can be seen that:The present embodiment can realize the controllable of the surface plasma body resonant vibration property of material
Regulation.
The present invention of embodiment 3 is adjusted to the method for embodiment 1:Added in the composite nano materials obtained in step (5)
The cuprous ion solution of ascorbic acid reduction, with the change of its addition, carries out absorption spectrum measurement, as a result such as Fig. 6
Shown (arrow is shown in Fig. 6 gradually increases the variation tendency of absorption spectrum with cuprous ion solution addition), can see
Arrive:The present embodiment can realize the reversible regulation and control of the surface plasma body resonant vibration property of material.
The present invention of embodiment 4 is adjusted to the method for embodiment 1:Added in the composite nano materials obtained in step (5)
Cuprous ion solution to its absorbent properties of ascorbic acid reduction no longer change, and then will remove the composite Nano material of cuprous ion
Material is exposed in air, and an absorption spectrum measurement is carried out every 30min during beginning, and mid-term is once inhaled every 1h
Spectral measurement is received, the later stage carries out an absorption spectrum measurement every 2h, and as a result (arrow is shown in Fig. 8 as shown in Figure 8
Gradually increase the variation tendency of absorption spectrum with the air exposure time), it can be seen that:The present embodiment repeated multiple times can be realized
The reversible controllable adjustment of the surface plasma body resonant vibration property of material.
The present invention of embodiment 5 is adjusted to the method for embodiment 1:Bar-shaped gold nano grain is prepared in set-up procedure (5)
The addition of experiment parameter, such as silver nitrate, reducing agent and gold seeds liquid, so that the size to bar-shaped gold nano grain is adjusted
Control, and then obtain the composite of different sizes.The gained composite nano materials of embodiment 5 have been carried out with transmission electron microscope point
Analysis, as a result as shown in Figure 10 a- Figure 10 h, it can be seen that:The present embodiment results in a series of answering for different sizes
Close nano material and be all uniformly distributed in core shell structure.The present invention is also to a series of different sizes prepared by embodiment 5
Composite nano materials have carried out ultraviolet-infrared vis spectroscopy spectrum analysis respectively, as a result as shown in figure 11, it can be seen that:It is logical
Cross and the size of composite nano materials is carried out regulating and controlling to realize to the controllable of the surface plasma body resonant vibration property of material
Regulation.
The embodiment of the present invention 6 of embodiment 6 provides a kind of composite nano materials, prepares in accordance with the following steps:
(1) first, gold seeds solution is prepared.At room temperature by chlorauric acid solution and cetyl trimethylammonium bromide solution
Stir, rapidly join the reducing agent sodium borohydride solution of ice bath preservation, 2min is persistently stirred, then at 25~30 DEG C
Under the conditions of stand 30min to 1h obtain gold seeds solution.Secondly, golden rod growth-promoting media is prepared.At room temperature by hexadecane
The base trimethylammonium bromide aqueous solution, silver nitrate solution and chlorauric acid solution stir, and then add reducing agent ascorbic acid molten
Liquid, lasting stirring is until solution is in colourless.Finally, a certain amount of gold seeds solution prepared is added in golden rod growth-promoting media,
10s is stirred, 8~12h is then stood under the conditions of 25~35 DEG C obtains bar-shaped gold nano grain;
(2) bar-shaped gold nano grain obtained by step (1) is centrifuged, removes supernatant liquor, be re-dispersed into poly dimethyl two
In allyl ammonium chloride solution, noble metal nano particles dispersion is formed;
(3) 10mmol selenium dioxide is added in dispersions, and ultrasonic disperse stirs 30min in protective atmosphere
30 DEG C are heated to, then 60mmol ascorbic acid is injected into dispersion, 10~20min is reacted, selenium is obtained and coats bar-shaped gold
The intermediate of nano particle;
(4) copper source mixed liquor is prepared:20mmol cupric sulfate pentahydrates and the mixing of 80mmol ascorbic acid.
(5) mixed liquor prepared by (4) is added into the solution containing intermediate obtained by step (3), protectiveness is maintained at
In atmosphere under 30 DEG C of heating stirrings, composite nano materials are obtained.
The present invention has carried out transmission electron microscope analysis to the gained composite nano materials of embodiment 6, as a result as shown in figure 3, can see
Arrive, the composite nano materials intersperse the structure and morphology of the uneven cladding bar-shaped gold nano grain of shape in copper selenide particle, illustrate logical
The regulation and control of appearance of nano material can be realized by overregulating surfactant.
The present invention of embodiment 7 is adjusted to the method for embodiment 6:Increase air open-assembly time in step (5), during beginning
An absorption spectrum measurement is carried out every 30min, mid-term carries out an absorption spectrum measurement every 1h, and the later stage is every 2h
An absorption spectrum measurement is carried out, as a result (arrow is shown in Fig. 5 gradually increases suction with the air exposure time as shown in Figure 5
Receive the variation tendency of spectrum), it can be seen that:The present embodiment is not only by changing material morphology but also by controlled material current-carrying
Sub- concentration realizes the controllable adjustment of surface plasma body resonant vibration property.
The present invention of embodiment 8 is adjusted to the method for embodiment 6:Added in the composite nano materials obtained in step (5)
The cuprous ion solution of ascorbic acid reduction, with the change of its addition, carries out absorption spectrum measurement, as a result such as Fig. 7
Shown (arrow is shown in Fig. 7 gradually increases the variation tendency of absorption spectrum with cuprous ion solution addition), can see
Arrive:The present embodiment can realize the reversible regulation and control of the surface plasma body resonant vibration property of material.
The present invention of embodiment 9 is adjusted to the method for embodiment 6:Added in the composite nano materials obtained in step (5)
Cuprous ion solution to its absorbent properties of ascorbic acid reduction no longer change, and then will remove the composite Nano material of cuprous ion
Material is exposed in air, and an absorption spectrum measurement is carried out every 30min during beginning, and mid-term is once inhaled every 1h
Spectral measurement is received, the later stage carries out an absorption spectrum measurement every 2h, and as a result (arrow is shown in Fig. 9 as shown in Figure 9
Gradually increase the variation tendency of absorption spectrum with the air exposure time), it can be seen that:The present embodiment repeated multiple times can be realized
The reversible controllable adjustment of the surface plasma body resonant vibration property of material.
The copper selenide nanoparticles that embodiment 10 takes 6 part of 800 μ L to be synthesized under the conditions of polyacrylic acid surfactant respectively are molten
Liquid, wherein 1 part as reference, the ascorbic acid of different volumes is separately added into other 5 parts of copper selenide nanoparticles solution
The cuprous ion solution of reduction, makes ultimate density of the concentration of cuprous ion in 5 parts of copper selenide nanoparticles solution be respectively
7.76×10-6mol/L、1.54×10-5mol/L、3.05×10-5mol/L、4.52×10-5mol/L、8.72×10-5mol/L、
1.39×10-4Mol/L, at room temperature act on 1 minute after, monitored in real time in Visible-to-Near InfaRed area, record its surface etc. from
Daughter resonance absorbance spectrum change curve, record result is as shown in figure 12.
Embodiment 11 takes 6 part of 800 μ L to coat copper selenide in bar-shaped gold nano grain under polyacrylic acid surfactant respectively
Composite nano materials solution, wherein 1 part as reference, not consubstantiality is separately added into other 5 parts of composite nano materials solution
The cuprous ion solution of long-pending ascorbic acid reduction, makes ultimate density of the concentration of cuprous ion in 5 parts of composite nano materials
Respectively 1.54 × 10-5mol/L、3.05×10-5mol/L、7.35×10-5mol/L、1.39×10-4mol/L、2.5×10-4mol/L、
4.81×10-4Mol/L, at room temperature act on 1 minute after, monitored in real time in Visible-to-Near InfaRed area, record its surface etc. from
Daughter resonance absorbance spectrum change curve, record result is as shown in figure 13.
The technology contents and technical characteristic of the present invention have revealed that as above, but those skilled in the art are still potentially based on this
Teaching and the announcement of invention and make a variety of replacements and modification without departing substantially from spirit of the present invention, therefore, the scope of the present invention should not
It is limited to the content disclosed in embodiment, and various replacements and modification without departing substantially from the present invention should be included, and is present patent application power
Profit requires to be covered.
Claims (13)
1. a kind of method that dynamic reversible regulates and controls surface plasma body resonant vibration property, it is characterised in that comprise the following steps:
(1)The nano material that dispersed chalcogen copper compound coats noble metal is prepared in protective atmosphere, the nano material includes the chalcogen copper compound of noble metal nano particles and the cladding noble metal nano particles;
(2)By step(1)The nano material exposure of preparation in atmosphere, and monitors the surface plasmon resonance absorption wavelength of the nano material, realizes the regulation and control to the surface plasma resonance property of the nano material;
(3)When the nano material by atmosphere be exposed to surface plasmon resonance absorption wavelength it is constant when, cuprous ion solution is added into the nano material, and after cuprous ion solution is added every time, the surface plasmon resonance absorption wavelength of the nano material is monitored, the reversible regulation and control to the surface plasma resonance property of the nano material are realized;
(4)Remove through step(3)The cuprous ion in the nano material after processing, and again expose the nano material in atmosphere, while monitoring the surface plasmon resonance absorption wavelength of the nano material, realize the reversible regulation and control to the surface plasma resonance property of the nano material.
2. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 1, it is characterised in that including:Repeat step(2)~step(4)Operation more than twice.
3. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 1, it is characterised in that:The chalcogen copper compound includes copper selenide or copper sulfide;And/or, the material of the noble metal nano particles includes any one in Au Ag Pt Pd, tin, cobalt and nickel or two or more combinations.
4. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 1, it is characterised in that the preparation method of the nano material of the chalcogen copper compound cladding noble metal includes:
In protective atmosphere, noble metal nano particles are scattered in deionized water, and add surfactant, nanoparticle dispersion is formed;
Protective atmosphere is maintained, while adding selenium source and/or sulphur source into the nanoparticle dispersion, reducing agent is added afterwards, the reaction system that noble metal nano particles intermediate is coated containing selenium and/or sulphur is obtained;
Copper source is added into the reaction system containing selenium and/or sulphur cladding noble metal nano particles intermediate to be reacted, and forms the nano material that the chalcogen copper compound coats noble metal.
5. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4, it is characterised in that including:Precious metal salt is scattered in the solvent containing surfactant, and the mixture to be formed is reached fluidized state, reducing agent is added, the noble metal nano particles are formed.
6. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 5, it is characterised in that including:During the noble metal nano particles are prepared, by the regulation and control to experiment parameter, the regulation and control of the particle size of noble metal nano particles are realized;The experiment parameter includes reducing agent, Ag+And combination more than any one of the consumption of seed liquor or both.
7. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4, it is characterised in that including:During the nanoparticle dispersion is prepared, by changing the type of the surfactant in nano material preparation process, the regulation and control to the appearance of nano material are realized.
8. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 1 or 4, it is characterised in that:The protective atmosphere is mainly formed by argon gas and/or nitrogen.
9. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4, it is characterised in that:Described selenium source includes selenium dioxide, sodium selenide or selenous acid;And/or, described sulphur source includes sulphur powder or lauryl mercaptan;And/or, described copper source includes copper sulphate, copper nitrate or copper chloride.
10. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4, it is characterised in that:The ratio between amount of material of selenium element is 1 in the amount of the material of copper and the selenium source in copper source:1~4:1;And/or, the ratio between amount of material of element sulphur is 1 in the amount of the material of copper and the sulphur source in copper source:1~4:1.
11. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4 or 5, it is characterised in that:The reducing agent includes any one or two or more combinations in ascorbic acid, sodium citrate, boron hydracid sodium.
12. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 4 or 5, it is characterised in that:The surfactant includes nonionic surface active agent or ionic surfactant, the nonionic surface active agent includes polyvinyl alcohol or polyethylene glycol, and the ionic surfactant includes any one or two or more combinations in neopelex, lauryl sodium sulfate, cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride.
13. dynamic reversible regulates and controls the method for surface plasma body resonant vibration property according to claim 1, it is characterised in that:The cuprous ion solution is selected from the cuprous ion solution that ascorbic acid is reduced.
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