CN105384176A - Prussian blue composite photonic crystal and preparing method and application thereof - Google Patents

Prussian blue composite photonic crystal and preparing method and application thereof Download PDF

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CN105384176A
CN105384176A CN201510742596.7A CN201510742596A CN105384176A CN 105384176 A CN105384176 A CN 105384176A CN 201510742596 A CN201510742596 A CN 201510742596A CN 105384176 A CN105384176 A CN 105384176A
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sio
photonic crystal
electrochromic material
microballoon
composite
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CN105384176B (en
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李昕
王锐
秦咪咪
廖佳星
张焱
郑一平
张德权
李文霞
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Beijing Institute Fashion Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/126—Preparation of silica of undetermined type
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

The invention belongs to the fields of chemical engineering and materials, and particularly relates to the field of the electrochromic material, in particular to a Prussian blue composite photonic crystal (composite membrane) and a preparing method and application thereof. More specifically, an inorganic electrochromic material SiO2 composite photonic crystal is provided. Preferably, the inorganic electrochromic material is Prussian blue. The composite photonic crystal has high electrochromism performance.

Description

Prussian blue composite photonic crystal, its preparation method and application
Technical field
The invention belongs to chemical industry and Material Field, particularly, belong to electrochromic material field.The present invention relates to a kind of inorganic electrochromic material-SiO 2composite photonic crystal, particularly, relates to the blue composite photonic crystal (composite membrane) of Shandong scholar, its preparation method and application.
Background technology
Electrochromism refers to that material is under the effect of impressed current or electric field, and the optical property of material produces stable reversible change in visible wavelength range, shows as the reversible change of the optical properties such as color in appearance.Electrochromic material, as the core component of device, is divided into inorganic electrochromic material and the large class of organic electrochromic material two usually.
There is between inorganic electrochromic material and organic electrochromic material very large difference.The variable color behavior of inorganic electrochromic material is that its contrast gradient is large, and stability is high, in smart window and electrochromic display device, therefore apply also commercialization because the Dual Implantations of ion and electronics and black soy sauce go out to cause.The variable color behavior of organic electrochromic material derives from their redox reaction, its colour-change is enriched, and carry out Optimal performance easily through change molecular structure, but also there are some shortcomings: as chemical stability and anti-good fortune penetrate ability, adhere to loosely etc. with substrate.Organic electrochromic material presses material structure roughly mainly polymer electrochromic material, and organic molecule electrochromic material.The part of inorganic electrochromic material and polymer electrochromic material is distinguished as shown in Table 1 below:
Table 1: inorganic with polymer electrochromic material property
Sequence number Performance Inorganic electrochromic material Conductive polymers
1 Preparation method Sophisticated technology Simple chemical polymerization
2 The workability of material Difference Easy processing
3 Equipment cost High Low
4 Color change interval Limited several colors Colourful color
5 Contrast gradient Relatively high Low
6 Time of response 10-750ms 10-120ms
7 Cycle life 1＊10 4-1＊10 6 1＊10 3-1＊10 5
Prussian blue (PrussianBlue, PB) inorganic electrochromic material is belonged to, it has unique tridimensional network, and the PB being in different oxidation state can present distinct colors, in addition, it also has excellent chemical property, electrochemical reversibility is fine, and stability is very high, and preparation cost is lower.
Photonic crystal (PhotonicCrystals, PC) be the artificial micro-structure arranged by the medium period of different refractivity, there is the characteristic of forbidden photon band, the light of certain wavelength in forbidden band can not through and reflected, thus present color corresponding with it.The color of photonic crystal display is schemochrome, compared with pigmentary colour, has high saturation, high brightness, will never fade special performance.
Counter opal structure is the structure of copying photonic crystal, filler between the space of photonic crystal, then eliminates original photon crystal micro-ball, and it is full of air on the position of original microballoon, thus makes itself and photon crystal structure just in time contrary.In addition, make counter opal structure also will the basis after compound substance further be calcined or etching processing, add application difficulty, and if the words that the structure of matter of filling is softer, the counter opal structure formed after eliminating microballoon is easy to cave in, its fixing complete shape cannot be kept, therefore also also can have a certain impact to its performance.
At present, need badly exploitation a kind of prepare simple and convenient, cost is low, the composite photonic crystal of good stability and preparation method thereof.
Summary of the invention
The present inventor, through deep research and performing creative labour, has obtained a kind of inorganic electrochromic material-SiO 2composite photonic crystal, particularly PB-SiO 2composite photonic crystal.The present invention has also obtained and has been applicable to preparation inorganic electrochromic material-SiO 2the SiO of composite photonic crystal 2microballoon, SiO 2photonic crystal and preparation method thereof.Thus provide following invention:
One aspect of the present invention relates to a kind of SiO 2microballoon, described SiO 2the median size of microballoon is 250-400nm, 280-370nm, 290-360nm, 300-350nm, 315-340nm, 320-335nm, 325-335nm or 330nm;
Preferably, described SiO 2microballoon is obtained by following step:
A. Virahol, water, ammoniacal liquor are mixed with suitable proportion, stirred by mixture and keep 65 DEG C-75 DEG C, more dropwise add tetraethoxy with the rotating speed of 350-450r/min, reaction is obtained;
Preferably, Virahol used: water: ammoniacal liquor: the volume ratio of tetraethoxy is (20-30): (4-6): (1-2): (2-4); More preferably, be (22-28): (4.5-5.5): (1.2-1.8): (2.5-3.5); Be particularly preferably 25:5:1.5:3.
Preferably, the concentration of ammoniacal liquor used is 25%-28% (mass concentration).
The present inventor find, when keep temperature lower be particularly low to moderate 60 DEG C time, obtained SiO 2microballoon size is uneven, and shape is undesirable.The experimental result of contrast preparation example 2 and embodiment 1 confirms above-mentioned discovery.
Preferably, described temperature is 68 DEG C-72 DEG C, 68 DEG C, 69 DEG C, 70 DEG C, 71 DEG C or 72 DEG C, or the temperature range that above-mentioned arbitrary two Temperature numerical are formed; Particularly preferably, be 70 DEG C.
Preferably, described rotating speed is 380-420r/min, 390-410r/min, 390r/min, 391r/min, 392r/min, 393r/min, 394r/min, 395r/min, 396r/min, 397r/min, 398r/min, 399r/min, 400r/min, 401r/min, 402r/min, 403r/min, 404r/min, 405r/min, 406r/min, 407r/min, 408r/min, 409r/min or 410r/min, or the speed range that above-mentioned arbitrary two speed revolution values are formed; Particularly preferably, be 400r/min.
Preferably, also step b is comprised:
B. the product in step a is used respectively water and ethanol centrifuge washing 1 time or repeatedly;
Be not limited to theoretical restriction, water is in order to the residual inorganics of microsphere surface removing, and ethanol is that washing dissolves organism.
Preferably, also step c is comprised:
C. SiO is obtained by dispersed in ethanol for the product in step b 2alcohol dispersion liquid.In baking oven, drying obtains SiO more afterwards 2powder.
Another aspect of the present invention relates to a kind of SiO 2the preparation method of photonic crystal, comprises the steps:
(1) dispersion medium is used, by the SiO of the invention described above 2microballoon is mixed with the SiO that concentration is 1.5mg/mL-2.5mg/mL 2monodisperse liquor;
(2) SiO is made by vertical sedimentation method 2depositing them is on substrate;
Preferably, also comprise,
(3) dispersion medium or until dispersion medium volatilizees completely is removed.
SiO according to any one of the present invention 2the preparation method of photonic crystal, is characterized in that following 1) to 4) any one in item or multinomial:
1) dispersion medium described in step (1) and step (3) is selected from ethanol, water and aqueous ethanolic solution; Described aqueous ethanolic solution is the aqueous solution of ethanol any concentration;
2) described in step (1), concentration is 1.8mg/mL-2.2mg/mL, 1.9mg/mL-2.1mg/mL, 1.8mg/mL, 1.9mg/mL, 2.0mg/mL, 2.1mg/mL or 2.2mg/mL;
3) system temperature in the vertical sedimentation process in step (2) is 35-45 DEG C, 38-42 DEG C, 38 DEG C, 39 DEG C, 40 DEG C, 41 DEG C or 42 DEG C;
4) the described substrate in step (2) is ito glass or FTO glass, preferably, also dry after ITO or FTO glass being used under ul-trasonic irradiation water, acetone and washes of absolute alcohol 15min successively.
The present inventor finds under study for action, works as SiO 2monodisperse liquor concentration for being less than 1.5mg/mL, time particularly close to 1mg/mL, obtained SiO 2there is a large amount of defect in photonic crystal, such as, has space to exist, and photonic crystal does not have large-area compact growth.Work as SiO 2monodisperse liquor concentration for being greater than 2.5mg/mL, time particularly close to 5mg/mL, obtained SiO 2photonic crystal is multilayer.In above-mentioned concentration range, the SiO of obtained individual layer 2photonic crystal.The experimental result of contrast preparation example 3 and embodiment 1 confirms above-mentioned discovery.
The present inventor also finds under study for action further, when system temperature in vertical sedimentation process in step (2) is lower than 35 DEG C, photonic crystal poor growth, likely becomes gravity sedimentation instead of vertical deposition, on the bottom that can be deposited on beaker instead of substrate; During higher than 45 DEG C, in photonic crystal process of growth, pull rate is too fast, and the photonic crystal obtained is uneven, and likely right and wrong are tightly packed.
Another aspect of the invention relates to a kind of SiO 2photonic crystal, it is by SiO of the present invention 2microballoon is formed; Described SiO 2microballoon is single or multiple lift; Preferably, described composite photonic crystal also comprises substrate; More preferably, described substrate is ito glass or FTO glass;
Preferably, described SiO 2photonic crystal is obtained by the foregoing preparation method of the present invention.
Another aspect of the invention relates to a kind of composite particles, and it comprises core and coating layer, and wherein, described core is SiO 2microballoon, described coating layer is inorganic electrochromic material;
Preferably, described SiO 2microballoon is SiO of the present invention 2microballoon;
Preferably, described coating layer is Prussian blue;
Preferably, the mean thickness of described coating layer is 35-60nm, be preferably 40-50nm, such as 40nm, 41nm, 42nm, 43nm, 44nm, 45nm, 46nm, 47nm, 48nm, 49nm, 50nm, or the thickness range that above-mentioned any two thickness value are formed; Be more preferably 44nm.
Another aspect of the invention relates to a kind of inorganic electrochromic material-SiO 2the preparation method of composite photonic crystal, comprises the steps:
With above-mentioned SiO of the present invention 2photonic crystal, as working electrode, makes inorganic electrochromic material be deposited into SiO by electrodip process in three-electrode system 2photonic crystal;
Preferably, it is characterized in that following 1)-4) any one in item or multinomial:
1) described inorganic electrochromic material is Prussian blue, and electrolytic solution is the PB solution of 2.0-3.0mmol/L, is preferably 2.2-2.8mmol/L or 2.4-2.6mmol/L, the PB solution of such as 2.4mmol/L, 2.5mmol/L or 2.6mmol/L;
2) being to electrode with platinum filament, take saturated calomel electrode as reference electrode;
3) galvanic deposit applied voltage is the constant voltage of 0.5-1.0V, preferred 0.6-0.8V, such as 0.6V, 0.7V or 0.8V;
4) electrodeposition time is 6-20 minute, is preferably 8-15 minute, 8-12 minute or 9-11 minute, such as 8 minutes, 9 minutes, 10 minutes, 11 minutes or 12 minutes.
The present inventor finds, when electrodeposition time is less than or equal to 5 minutes, inorganic electrochromic material can the surface of coated silica microballoon completely.The experimental result of contrast preparation example 4 and embodiment 1 confirms above-mentioned discovery.
In the present invention's preferred embodiment, described inorganic electrochromic material is Prussian blue, and platinum filament is to electrode, and saturated calomel electrode is reference electrode, with the PB solution of 2.5mmol/L for electrolytic solution, and galvanic deposit 10 minutes under the constant voltage of 0.7V.
Another aspect of the invention relates to a kind of inorganic electrochromic material-SiO 2composite photonic crystal, preferably, described inorganic electrochromic material is Prussian blue; Particularly, it is made up of the composite particles of the invention described above;
Preferably, described composite photonic crystal also comprises substrate; More preferably, described substrate is ito glass or FTO glass;
Preferably, it is obtained by above-mentioned preparation method of the present invention.
The present invention improves Prussian blue electrochromic property by introducing silicon-dioxide photon crystal structure.Make the cyclic voltammetric performance of PB, square wave scan performance is greatly increased, thus the application of expansion PB.The present invention also improves Prussian blue optical property by introducing silicon-dioxide photon crystal structure, its colour-change brightness and saturation ratio are increased, and contrast color change increases.PB-SiO 2photonic crystal color homogeneity significantly improves.
The present invention utilizes electrochemical workstation and ultraviolet-visible light spectrometer to test PB-SiO 2the reflection spectrum of photon crystal film, cyclic voltammetry curve, many current potentials ultra-violet absorption spectrum, optics, electrochemistry and the electrochromic property such as contrast gradient and time of response.And with these performances for illustration understands that the electrochromic property of laminated film significantly improves.
Another aspect of the invention relates to a kind of composition, and it comprises SiO of the present invention 2microballoon, SiO of the present invention 2photonic crystal, composite particles of the present invention or inorganic electrochromic material-SiO of the present invention 2composite photonic crystal; Particularly, described composition is electrochromic material; More specifically, be electrochomeric films.
Another aspect of the invention relates to a kind of electrochromic device, and it is by SiO of the present invention 2microballoon, SiO of the present invention 2photonic crystal, composite particles of the present invention, inorganic electrochromic material-SiO of the present invention 2composite photonic crystal or composition of the present invention are made; Particularly, described electrochromic device is display device, information recording device, tunable reflectivity automobile rearview mirror, smart window, biosensor, chemical sensor, battery electrode or electro catalytic electrode.
Another aspect of the invention relates to SiO of the present invention 2microballoon, SiO of the present invention 2photonic crystal, composite particles of the present invention or inorganic electrochromic material-SiO of the present invention 2composite photonic crystal is preparing the purposes in electrochromic material or electrochromic device; Particularly, described electrochromic material is electrochromic material of the present invention; Particularly, described electrochromic device is electrochromic device of the present invention.
PB-SiO 2photon crystal film can be applied to the aspects such as photochromic and electrochromism.H can be detected as the electrochromic layer in electrochromic device, use PB modified electrode 2o 2with the electrode materials of the dyestuff of glucose etc., schemochrome, battery, electrocatalytic reaction (be such as deposited on form modified electrode above electrode carry out electrocatalysis) etc.
Except ito glass and FTO glass, also can with other conducting material as substrate, such as, when needs are applied on electrode, can choice electrode as the first deposit photon crystal of substrate, then compound PB.
Owing to wherein there being the existence of photonic crystal, so the form of its film must be kept.The thickness of film can be controlled by the control number of plies of photonic crystal and the depositing time of PB.The number of plies of photonic crystal is more, and the time of PB electrochemical deposition is longer, and film is thicker.
For PB-SiO of the present invention 2photonic crystal, the present inventor has also carried out reflection spectrum research, and result shows its forbidden photon band position at 575nm, namely visible region, and therefore, it can demonstrate specific color, is more conducive to the abundant change of color.Be not limited to theoretical restriction, may be less relevant with the particle diameter of silicon-dioxide photonic crystal.When silicon-dioxide photonic crystal particle diameter increases to more than 500nm, forbidden photon band may drop on near-infrared region.
In the present invention, term ito glass refers to indium oxide tin glass, and FTO glass refers to the SnO of doped with fluorine 2transparent conducting glass.
The beneficial effect of the invention
Inorganic electrochromic material-SiO of the present invention 2composite photonic crystal is PB-SiO particularly 2the colour-change brightness of photonic crystal and saturation ratio increase, and contrast color change increases, and particularly color homogeneity significantly improves, and color change speeds.
Accompanying drawing explanation
Fig. 1: Figure 1A, SiO 2the scanning electron microscope (SEM) photograph of photonic crystal; Magnification is 30,000 times, takes, operating distance 7.9mm under the beam voltage of 10.0KV.Figure 1B is the cross-sectional view of Figure 1A sample; Magnification is 30,000 times, takes, operating distance 7.4mm under the beam voltage of 10.0KV.
Fig. 1 C, PB-SiO 2the scanning electron microscope (SEM) photograph of composite photonic crystal; Magnification is 40,000 times, takes, operating distance 8.4mm under the beam voltage of 5.0KV.Fig. 1 D is the cross-sectional view of Fig. 1 C sample; Magnification is 20,000 times, takes, operating distance 8.5mm under the beam voltage of 10.0KV.
Fig. 1 E and Fig. 1 F, the obtained contrast SiO of contrast preparation example 2 2the scanning electron microscope (SEM) photograph of photonic crystal and control sample 2-1 and 2-2 (two batches under same process).Fig. 1 E magnification is 20,000 times, takes, operating distance 9.1mm under the beam voltage of 10.0KV.Fig. 1 F magnification is 40,000 times, takes, operating distance 10.3mm under the beam voltage of 10.0KV.
Fig. 1 G, the contrast SiO that contrast preparation example 3 is obtained when silica concentration is 1mg/mL 2the scanning electron microscope (SEM) photograph of photonic crystal and control sample 3-1; Magnification is 40,000 times, takes, operating distance 9.0mm under the beam voltage of 10.0KV.
Fig. 1 H, the contrast SiO that contrast preparation example 3 is obtained when silica concentration is 5mg/mL 2the scanning electron microscope (SEM) photograph of photonic crystal and control sample 3-2; Magnification is 30,000 times, takes, operating distance 7.9mm under the beam voltage of 10.0KV.Fig. 1 I is the cross-sectional view of Fig. 1 H sample; Magnification is 30,000 times, takes, operating distance 9.0mm under the beam voltage of 10.0KV.
Fig. 1 J to be the time of galvanic deposit PB be PB-SiO of 5 minutes 2the scanning electron microscope (SEM) photograph of composite photonic crystal and control sample 4-1.Magnification is 50000 times, takes, operating distance 9.5mm under the beam voltage of 5.0KV.
Fig. 2: Fig. 2 A, SiO 2the XRD analysis spectrogram of photonic crystal.Fig. 2 B, PB-SiO 2the XRD analysis spectrogram of photonic crystal.
Fig. 3: Fig. 3 A, PB film and PB-SiO 2the cyclic voltammetry curve of laminated film.Fig. 3 B, PB film and PB-SiO 2the colour-change of laminated film.Between-0.4V ~ 0V, film mainly shows shallow white, film is in the white structure in Prussian, along with the increase of voltage, film is in Prussian blue state, show blue between 0V ~ 0.6V and deepen gradually, the medium blue of 0.6V ~ 1.0V slowly shoals again, demonstrates khaki color between 1.0V ~ 1.4V, corresponding to the state of Prussian's Huang.Note: in order to meet the requirement of patent examination for color, gray proces has been carried out to Fig. 3 B.
Fig. 3 C, SiO 2the colour-change of PANI photonic crystal.Note: Fig. 3 C has carried out the gray proces same with Fig. 3 B.Although carried out gray proces, the colour inhomogeneous of PANI film can be found out, different with surrounding in the middle of picture.
Fig. 4: Fig. 4 A, many current potentials uv absorption spectra of pure PB film.Fig. 4 B, thin PB-SiO 2many current potentials uv absorption spectra of photon crystal film.
Fig. 5: Fig. 5 A, pure PB film is m-transmittance curve when the square-wave test of 694nm.Fig. 5 B, PB-SiO 2m-transmittance curve during the square-wave test of photon crystal film under 682nm.
Fig. 6: Fig. 6 A, pure PB film is at the cycle life-transmittance curve of 694nm.Fig. 6 B:PB-SiO 2cycle life-the transmittance curve of photon crystal film under 682nm.Tb is the transmitance of fading under state, and Tc is the transmitance of coloured state, and Δ T is maximum countrast.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting scope of the present invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Reagent and instrument
Tetraethoxy (TEOS, AR, Tong Guang fine chemistry industry company of Beijing); Virahol ((CH 3) 2cHOH, AR, Beijing Chemical Plant); Ethanol (C 2h 5oH, AR, Beijing Chemical Plant); Ammoniacal liquor (massfraction 25% ~ 28%, AR, Beijing Chemical Plant); The Tripotassium iron hexacyanide (AR, Beijing Chemical Plant); FERRIC CHLORIDE ANHYDROUS (CP, Chemical Reagent Co., Ltd., Sinopharm Group); Repone K (AR, Beijing Chemical Plant).Experimental water is deionized water.Ito glass, surface resistivity is 10 ~ 20 Ω/cm 2, respectively with deionized water, acetone and EtOH Sonicate cleaning 15min before using, nitrogen dries up.
Opal structural SiO 2film and PB-SiO 2the surface topography of photonic crystal adopts Japanese JEOL company JSM-6360LV type electron microscope to observe; Its XRD analysis adopts Rigaku RigakuD/MAX-2400 type x-ray diffractometer to measure; The test of electrochemical synthesis and cyclic voltammetry curve adopts German Zahner company IM6 type electrochemical workstation; Many current potentials uv absorption property of film and the test of time of response are by ZahnerIM6 type electrochemical workstation and U.S. PE company Lambda750 ultraviolet-visible light spectrometer is online makes for completing.
preparation example 1:SiO 2 the preparation of photonic crystal
Virahol: water: ammoniacal liquor: tetraethoxy (TEOS)=25:5:1.5:3 (volume ratio).
First Virahol, water, ammoniacal liquor are mixed with aforementioned proportion, stir with the constant rotational speed of 400r/min at the temperature of 70 DEG C and three is mixed, more dropwise add tetraethoxy, and react 5 hours under the stirring velocity kept above and temperature.After reaction terminates, by the SiO of gained 2microsphere suspension liquid uses water and ethanol centrifuge washing repeatedly (such as respectively to wash three times with water and ethanol), the SiO finally obtained respectively 2microballoon is dispersed in ethanol obtains SiO 2alcohol dispersion liquid.In baking oven, drying obtains SiO more afterwards 2powder and SiO 2microballoon (also selects suitable SiO by being purchased 2microballoon, with the preparation of photonic crystal later, but preferred method of the present invention prepares SiO 2microballoon).
Then vertical deposition method self-assembly SiO is adopted 2photonic crystal, under the condition of certain humiture, by the SiO obtained 2microballoon arranges in the deposition that ito glass surface uniform is neat, namely obtains the SiO of opal structural 2photonic crystal.Particularly, following steps are adopted:
After ito glass is used water, acetone and washes of absolute alcohol 15min successively under ul-trasonic irradiation, dry in Constant Temp. Oven.Make the SiO of dispersion medium preparation 2mg/mL with 40mL ethanol in each beaker 2monodisperse liquor, ultrasonic 15min is uniformly dispersed.Two panels ito glass is hung in each beaker.Afterwards beaker is placed in 40 DEG C of thermostat container fixed temperature and humidity 3-4 days, until the complete volatile dry of ethanol, namely can forms one deck SiO on ito glass surface 2crystal film and SiO 2photonic crystal.
SiO 2the number of plies of photonic crystal is particular by SiO in control dispersion system 2the amount of microballoon controls.We have done experiment for several times, and the amount determining 2mg/mL can control SiO 2the photonic crystal growth number of plies is one deck.Can find out to only have one deck intuitively from SEM figure.The present inventor also finds in further studying, and individual layer is more conducive to PB the complete coated Si O of time enough in the process of electrochemical deposition 2microballoon.And likely occur not exclusively coated when multilayer, only some PB particle is attached to the situation of microsphere surface.
preparation example 2:PB-SiO 2 the preparation of photonic crystal
PB-SiO 2the galvanic deposit of photonic crystal completes in three-electrode system.
Reagent: PB nano particle.Can be purchased, such as, label purchased from Chemical Reagent Co., Ltd., Sinopharm Group is the PB of 71034644.Also can be prepared with reference to methods known in the art, such as, with reference to method preparation below:
Use the 5mmol/LFeCl of 10mL 3, 10mL 5mmol/LK 3fe (CN) 6, the two all uses the KCl solution preparation of 0.1mol/L.First by the 5mmol/LFeCl of 10mL during reaction 3solution is poured in beaker, utilizes 0.01mol/LHCl adjust ph to be 2, then adds the 5mmol/LK of 10mL 3fe (CN) 6solution.Namely the two reaction generates PB particle.
SiO is had with the surface alignment that preparation example 1 is above obtained 2the ito glass of microballoon photonic crystal is working electrode, be to electrode and reference electrode with 1mm platinum filament and saturated calomel electrode respectively, with the PB solution of 2.5mmol/L for electrolytic solution (or preparing the reaction soln of PB nano particle for electrolytic solution above can directly using).Galvanic deposit 10 minutes under the constant voltage of 0.7V, then washes the residual particles on surface off, just obtains PB-SiO with deionized water 2photonic crystal of opals structure film.15min is dried at 72 DEG C, with embodiment 1-6 later with baking oven.
contrast preparation example 1: the preparation (control sample 1-1) of control sample PB film
In addition, under the experiment condition parallel with preparation example 2, with simple ito glass for working electrode prepares PB film (control sample 1-1).With embodiment 3-6 later.
contrast preparation example 2: contrast SiO 2 the preparation (control sample 2-1 and 2-2) of photonic crystal
According to the experiment condition that preparation example 1 is identical, except temperature is adjusted to 60 DEG C by 70 DEG C.
Obtained contrast SiO 2photonic crystal and control sample 2-1 and 2-2 (two batches under same process).
contrast preparation example 3: contrast SiO 2 the preparation (control sample 3-1 and 3-2) of photonic crystal
According to the experiment condition that preparation example 1 is identical, except to SiO 2the concentration of monodisperse liquor adjusts.When 1mg/mL, obtained contrast SiO 2photonic crystal and control sample 3-1; When 5mg/mL, obtained contrast SiO 2photonic crystal and control sample 3-2.
contrast preparation example 4: contrast PB-SiO 2 the preparation (control sample 4-1) of photonic crystal
Carry out with reference to the experiment condition in preparation example 2, wherein just galvanic deposit is adjusted to 5 minutes.
Obtained contrast PB-SiO 2photonic crystal (control sample 4-1).
embodiment 1: scanning electron microscopic observation
Japan JEOL company JSM-6360LV type electron microscope.
Sample is as follows:
The SiO that preparation example 1 is above obtained 2the PB-SiO that photonic crystal, preparation example 2 are obtained 2composite photonic crystal; And
The control sample 4-1 that control sample 3-1 and 3-2 that control sample 2-1 and 2-2 that the control sample 1-1 that contrast preparation example 1 above obtains, contrast preparation example 2 obtain, contrast preparation example 3 obtain, contrast preparation example 4 are obtained.
Result as shown in Figure 1.
As can be seen from Figure 1A, SiO 2microspherulite diameter is on average about 330nm, in the same size, on ito glass surface with hexagonal structure proper alignment.Cross-sectional view and Figure 1B of Figure 1A sample describe SiO from the side 2the number of plies of photonic crystal only has one deck.
With the photonic crystal after PB compound as shown in Figure 1 C, we can see that PB nano particle has sticked to the surface of silicon dioxide microsphere equably by galvanic deposit, its particle diameter is approximately 418nm (can be considered as film thickness), illustrates that the thickness of PB layer is about 44nm.And the laminated film obtained as seen from the figure still remains the structure of proper alignment.Fig. 1 D is the cross-sectional view of Fig. 1 C sample, and the number of plies describing the photonic crystal of composite membrane only has one deck.
In addition, the present inventor also finds under study for action:
1) size contrasting preparation example 2 silicon dioxide microsphere obtained at 60 DEG C is uneven, and shape is undesirable, as Fig. 1 E and Fig. 1 F.
2) contrast preparation example 3 when silica concentration is 1mg/mL, silicon-dioxide photonic crystal has a large amount of defect to be existed, and as Fig. 1 G, can see and have space to exist, photonic crystal does not have large-area compact growth.When silica concentration is 5mg/mL, the photonic crystal growth number of plies is multilayer, as Fig. 1 H and Fig. 1 I, can find out that its number of plies is multilayer from the space of photonic crystal the first layer and cross-sectional view.
3) the contrast PB-SiO that preparation example 4 is obtained is contrasted 2photonic crystal sample, PB can the surface (Fig. 1 J) of silicon dioxide microsphere in complete coated sample.
embodiment 2:X ray diffraction experiments
Rigaku RigakuD/MAX-2400 type x-ray diffractometer.
Sample is the SiO that preparation example 1 above obtains 2the PB-SiO that photonic crystal and preparation example 2 obtain 2composite photonic crystal.
Result is as shown in accompanying drawing 2A and 2B.
Can see that from Fig. 2 A 2 θ have occurred amorphous diffraction peak at about 24 °, show the SiO synthesized by prepared example 1 2photonic crystal is amorphous solid particle, i.e. monodispersed SiO 2particle is amorphous structure.
Also SiO is there is in Fig. 2 B 2wider diffraction peak, and diffraction peak 28.5 °, 35.3 ° and 40.7 ° corresponding be PB (220), (400) and (420) crystal face respectively.Show Prussian blue successfully at silicon dioxide microsphere surface deposition.
embodiment 3: cyclic voltammetry
1. laboratory apparatus and sample
Adopt German Zahner company IM6 type electrochemical workstation.
Sample is the PB-SiO that preparation example 2 obtains 2the PB film that composite photonic crystal and contrast preparation example 1 obtain.
2. experimental technique
Electric potential scanning scope-0.2V-1.2V.
Being determined in three-electrode system of cyclic voltammetry curve completes.Electrolytic solution is the KCl solution of 0.1mol/L.To have the ito glass of PB film for working electrode, 1mm platinum filament and saturated calomel electrode are respectively electrode and reference electrode.The parameter of electrochemical workstation is: sweep limit-0.2V-1.2V, scanning speed 50mV/s, range of current-100mA-100mA.
3. experimental result
As shown in figs. 3 a and 3b.Fig. 3 A and Fig. 3 B is respectively PB film and PB-SiO 2the cyclic voltammetry curve of laminated film, and PB film and PB-SiO 2the colour-change of laminated film.
As can be seen from the figure, two CV curves have identical variation tendency, have two pairs of redox peaks, and the first pair of peak is that PB obtains electron reduction and becomes Prussian white (PW), and enters PB film lattice along with potassium ion.The second pair of peak is that PB loses electrons oxidizes and becomes Prussian's Huang (PY), and to move out PB film lattice along with potassium ion.The position at pure PB film two pairs of peaks is-0.08V/0.35V and 0.65V/0.98V respectively.PB-SiO 2composite membrane be 0V/0.3V and 0.75V/1.0V.But can PB-SiO be found out 2large than pure PB film of the electric current of film and area, illustrates PB-SiO 2the chemical property of crystal film with photon is better than pure PB film.
In redox processes, PB film and PB-SiO 2the colour-change comparing class of laminated film seemingly, but PB-SiO 2the color of laminated film is more beautiful than the color of PB film, and has the gloss as metal.Between-0.4V ~ 0V, film mainly shows shallow white, film is in the white structure in Prussian, along with the increase of voltage, show blue between 0V ~ 0.6V and deepen gradually, the medium blue of 0.6V ~ 1.0V slowly shoals again, khaki color is demonstrated, corresponding to the state of Prussian's Huang between 1.0V ~ 1.4V.
In addition, SiO was once early stage in the seminar at the present inventor place 2the research of PANI photonic crystal and exploration, but unfortunately find SiO 2pANI photonic crystal shows the situation (Fig. 3 C) of uneven color.And PB-SiO of the present invention 2photonic crystal color even.Be not limited to theoretical restriction, SiO 2the color homogeneity of PANI photonic crystal is not good, is likely SiO 2microspherulite diameter not evenly and be arranged in photonic crystal process arrange neat not caused by, and in the process of electrochemical polymerization PANI, also can cause the uneven distribution of PANI.This also illustrates SiO prepared by the present invention 2photonic crystal performance improves.
embodiment 4: many current potentials ultra-violet absorption spectrum is tested
1. experiment purpose:
Wavelength to be determined time in order to determine that square wave scans.Under maximum absorption wavelength, measure square wave scanning can obtain maximum contrast gradient.
2. laboratory apparatus and sample
ZahnerIM6 type electrochemical workstation and the online use of U.S. PE company Lambda750 ultraviolet-visible light spectrometer.
Sample is the PB-SiO that preparation example 2 obtains 2the PB film that composite photonic crystal and contrast preparation example 1 obtain.
3. experimental technique
In ultraviolet-visual spectrometer, put into the cuvette of the KCl solution filling 0.1mol/L, be that container arranges three-electrode system with cuvette.To have the ito glass of PB film for working electrode, 1mm platinum filament and saturated calomel electrode are respectively electrode and reference electrode.Electrochemical workstation is responsible for applying constant different voltage, voltage range-0.2V-1.2V to working electrode, gets a numerical value every 0.2V.When after the voltage stabilization applied, select absorbance A, use ultraviolet-visual spectrometer carries out the length scanning within the scope of 400nm-800nm.
4. experimental result
As shown in accompanying drawing 4A and 4B.
As can be seen from Fig. 4 A, the maximum absorption wavelength of pure PB film, in Prussian has the absorption peak that wide, belongs to the charateristic avsorption band of PB, correspond to Fe in PB when white and Prussian blue state in the structure of 694nm, PB film at 694nm place 2+to Fe 3+between Charger transfer, along with Prussian blue this peak yellow, Prussian that is transformed into fades away.Comparison diagram 4B can see, PB-SiO 2the absorption spectrum of laminated film with the situation of voltage change and pure PB film similar.The maximum absorption wavelength of laminated film is at 682nm.
embodiment 5: square wave electric potential scanning is tested
1. laboratory apparatus and sample
ZahnerIM6 type electrochemical workstation and the online use of U.S. PE company Lambda750 ultraviolet-visible light spectrometer.
Sample is the PB-SiO that preparation example 2 obtains 2the PB film that composite photonic crystal and contrast preparation example 1 obtain.
2. experimental technique
By electrochemical workstation and ultraviolet-visible spectrometer online, in the Klorvess Liquid of 0.1mol/L, carry out the test of square wave electric potential scanning.When testing, choose the voltage that-0.2V and 0.6V is respectively its reduction-state and oxidation state, each holding time of voltage is 20s, and choosing the time of contrast gradient change needed for 90% is the time of response.
3. experimental result
Result as shown in Figure 5.Fig. 5 is PB-SiO 2m-transmittance curve during square-wave test respectively under 694nm and 682nm of photon crystal film and pure PB film.
Be can be calculated by Fig. 5, PB-SiO 2the maximum countrast Δ Tmax of photon crystal film is 49.1%, its painted and time of response of fading is respectively 3.4s and 6.1s (Fig. 5 A), and the Δ Tmax of pure PB film is 32.2%, its painted and time of response of fading is respectively 7.6s and 14.3s (Fig. 5 B).
Visible, PB-SiO 2the optical contrast of photon crystal film is higher than pure PB film, and the time of response is shorter.
Result of study shows, gained PB-SiO 2redox ability and the pure PB of photonic crystal are much the same; Compared to the contrast gradient of pure PB film 32.2%, this photon crystal film maximum countrast increases, and reaches 49.1%; PB-SiO 2painted and the time of response of fading of photon crystal film is respectively 3.4s and 6.1s, pure PB is respectively 7.6s and 14.3s, painted and the time of response of fading shortens greatly, amplitude is all more than 55%, this is very significant, and so large amplitude is also the unforeseeable technique effect of those skilled in the art.Result of study shows, by SiO 2photon crystal structure introduces mineral-type conductive polymers particularly in PB, can obtain high performance electrochromic material.
embodiment 6: cyclical stability is tested
1. laboratory apparatus and sample
ZahnerIM6 type electrochemical workstation and the online use of U.S. PE company Lambda750 ultraviolet-visible light spectrometer.
Sample is the PB-SiO that preparation example 2 obtains 2the PB film that composite photonic crystal and contrast preparation example 1 obtain.
2. experimental technique
By electrochemical workstation and ultraviolet-visible spectrometer online, in the Klorvess Liquid of 0.1mol/L, carry out the test of square wave electric potential scanning.When testing, choose the voltage that-0.2V and 0.6V is respectively its reduction-state and oxidation state, each holding time of voltage is 20s, test 200 circulation number of turns, and go a numerical point (Tb, Tc and Δ T) every 10 circles, obtain the cycle life figure in accompanying drawing.
3. experimental result
Result as shown in Figure 6.Fig. 6 is PB-SiO 2photon crystal film and the pure PB film cycle life-transmittance curve respectively under 694nm (Fig. 6 A) and 682nm (Fig. 6 B).
As can be seen from the figure, PB film has dropped to 55.61 from 62.24 after-0.2V scanning 200 circle, reduces 6.63%, and PB-SiO 2film increases 88.98 from 78.76, adds 10.22%.When applying voltage is 0.6V, the transmitance of PB film remains unchanged substantially, increases a little to some extent.PB-SiO 2film increases 37.91 from 26.53, adds 11.38%.The contrast gradient Δ T-phase of the two than the increase can found out along with the circulation number of turns, the Amplitude Ratio PB-SiO that the Δ T of PB film reduces 2large many (having dropped to 27.22% from 34.83%), and PB-SiO 2Δ T substantially remain unchanged.This illustrates that the cyclical stability of laminated film is better than pure PB film, and tested to determine environmental influence little.
Although the specific embodiment of the present invention has obtained detailed description, it will be understood to those of skill in the art that.According to disclosed all instructions, can carry out various amendment and replacement to those details, these change all within protection scope of the present invention.Four corner of the present invention is provided by claims and any equivalent thereof.

Claims (10)

1. a SiO 2microballoon, described SiO 2the median size of microballoon is 250-400nm, 280-370nm, 290-360nm, 300-350nm, 315-340nm, 320-335nm, 325-335nm or 330nm;
Preferably, described SiO 2microballoon is obtained by following step:
Virahol, water, ammoniacal liquor are mixed with suitable proportion, stirred by mixture and keep 65 DEG C-75 DEG C, more dropwise add tetraethoxy with the rotating speed of 350-450r/min, reaction is obtained;
Preferably, Virahol used: water: ammoniacal liquor: the volume ratio of tetraethoxy is (20-30): (4-6): (1-2): (2-4); Be more preferably 25:5:1.5:3.
2. a SiO 2the preparation method of photonic crystal, comprises the steps:
(1) dispersion medium is used, by the SiO described in claim 1 2microballoon is mixed with the SiO that concentration is 1.5mg/mL-2.5mg/mL 2monodisperse liquor;
(2) SiO is made by vertical sedimentation method 2depositing them is on substrate;
Preferably, also comprise,
(3) dispersion medium or until dispersion medium volatilizees completely is removed.
3. preparation method according to claim 2, is characterized in that following 1) to 4) any one in item or multinomial:
1) dispersion medium described in step (1) and step (3) is selected from ethanol, water and aqueous ethanolic solution;
2) described in step (1), concentration is 1.8mg/mL-2.2mg/mL, 1.9mg/mL-2.1mg/mL, 1.8mg/mL, 1.9mg/mL, 2.0mg/mL, 2.1mg/mL or 2.2mg/mL;
3) system temperature in the vertical sedimentation process in step (2) is 35-45 DEG C, 38-42 DEG C, 38 DEG C, 39 DEG C, 40 DEG C, 41 DEG C or 42 DEG C;
4) the described substrate in step (2) is ito glass or FTO glass, preferably, also dry after ito glass or FTO glass being used under ul-trasonic irradiation water, acetone and washes of absolute alcohol 15min successively.
4. a SiO 2photonic crystal, it is by SiO according to claim 1 2microballoon is formed; Described SiO 2microballoon is single or multiple lift; Preferably, described composite photonic crystal also comprises substrate; More preferably, described substrate is ito glass or FTO glass;
Preferably, described SiO 2photonic crystal is obtained by the preparation method described in Claims 2 or 3.
5. a composite particles, it comprises core and coating layer, and wherein, described core is SiO 2microballoon, described coating layer is inorganic electrochromic material;
Preferably, described SiO 2microballoon is SiO according to claim 1 2microballoon;
Preferably, described coating layer is Prussian blue;
Preferably, the mean thickness of described coating layer is 35-60nm, is preferably 40-50nm; Be more preferably 44nm.
6. an inorganic electrochromic material-SiO 2the preparation method of composite photonic crystal, comprises the steps:
With SiO according to claim 4 2photonic crystal, as working electrode, makes inorganic electrochromic material be deposited into SiO by electrodip process in three-electrode system 2photonic crystal;
Preferably, it is characterized in that following 1)-4) any one in item or multinomial:
1) described inorganic electrochromic material is Prussian blue, and electrolytic solution is the PB solution of 2.0-3.0mmol/L, is preferably 2.2-2.8mmol/L or 2.4-2.6mmol/L, the PB solution of such as 2.4mmol/L, 2.5mmol/L or 2.6mmol/L;
2) being to electrode with platinum filament, take saturated calomel electrode as reference electrode;
3) galvanic deposit applied voltage is the constant voltage of 0.5-1.0V, preferred 0.6-0.8V, such as 0.6V, 0.7V or 0.8V;
4) electrodeposition time is 5-20 minute, is preferably 8-15 minute or 8-12 minute, such as 8 minutes, 9 minutes, 10 minutes, 11 minutes or 12 minutes.
7. an inorganic electrochromic material-SiO 2composite photonic crystal, preferably, described inorganic electrochromic material is Prussian blue; Particularly, it is made up of composite particles according to claim 5;
Preferably, described composite photonic crystal also comprises substrate; More preferably, described substrate is ito glass or FTO glass;
Preferably, it is obtained by preparation method according to claim 6.
8. a composition, it comprises SiO according to claim 1 2microballoon, SiO according to claim 4 2photonic crystal, composite particles according to claim 5 or inorganic electrochromic material-SiO according to claim 7 2composite photonic crystal; Particularly, described composition is electrochromic material; More specifically, be electrochomeric films.
9. an electrochromic device, it is by SiO according to claim 1 2microballoon, SiO according to claim 4 2photonic crystal, composite particles according to claim 5, inorganic electrochromic material-SiO according to claim 7 2composite photonic crystal or composition according to claim 8 are made; Particularly, described electrochromic device is display device, information recording device, tunable reflectivity automobile rearview mirror, smart window, biosensor, chemical sensor, battery electrode or electro catalytic electrode.
10. SiO according to claim 1 2microballoon, SiO according to claim 4 2photonic crystal, composite particles according to claim 5 or inorganic electrochromic material-SiO according to claim 7 2composite photonic crystal is preparing the purposes in electrochromic material or electrochromic device; Particularly, described electrochromic material is electrochromic material according to claim 8; Particularly, described electrochromic device is electrochromic device according to claim 9.
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