CN113957539A - Photonic crystal material with large band gap modulation effect and organic environment stability as well as preparation method and application thereof - Google Patents
Photonic crystal material with large band gap modulation effect and organic environment stability as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a photonic crystal material with a large band gap modulation effect and organic environment stability, which is a PEDOT photonic crystal with an inverse opal structure. The photonic crystal material has a large band gap modulation effect and can be stably stored in an organic solvent for a long time. The invention also discloses a preparation method and application of the photonic crystal material.
Description
Technical Field
The invention relates to the field of photonic crystal materials. More particularly, relates to a photonic crystal material with large band gap modulation effect and organic environment stability, and a preparation method and application thereof.
Background
The photonic crystal is an artificial microstructure formed by periodically arranging media with different refractive indexes. The most essential features of photonic crystals are photon forbidden bands and photon localization. The photonic band gap can control the propagation of light in the photonic band gap, and the introduction of a defect state can influence the property of the photonic band gap, so that the photonic band gap is a key basic material for photoelectric integration, photonic integration and optical communication. At present, the application of the photonic crystal mainly focuses on photonic crystal high-performance devices, including high-sensitivity detection and sensing, high-efficiency catalysis, high-performance display, low-threshold laser and the like. The photonic crystal structure for preparing novel materials usually adopts a 'sacrificial template method'. The brief steps are: the photonic crystal with the opal structure is prepared as a template by a self-assembly method, then another material is filled in gaps of small spheres of the photonic crystal template, and finally the small spheres in the photonic crystal template are removed by means of solvent dissolution or high-temperature calcination to obtain the photonic crystal with the inverse opal structure. The method is simple, convenient and fast, has strong universality, and can be used for preparing inverse opal photonic crystals of any material.
PEDOT is a typical thiophene derivative, and a large pi-electron conjugated system exists in a polymer molecule, so that delocalization and migration between carriers and free electrons can be realized. Compared with other substituted polythiophenes, PEDOT has better backbone molecular coplanarity, and the conductivity of the oxidation doping state of the PEDOT is as high as 10-12-104S/cm and the conductivity is enhanced and stabilized by the polymer in the oxidized doped state. The PEDOT film has the characteristics of high conductivity, stable chemical property, high transparency, good environmental stability and the like, and is widely applied to photoelectric devices such as solar cells, sensors, supercapacitors, electrochromism and the like at present.
At present, in the existing research on the PEDOT photonic crystal, Lacriox et al mainly research the influence of the polymerization potential time of the PEDOT photonic crystal on the appearance and performance of a crystal structure in the electropolymerization process; the PEDOT/Ppy double-layer composite antitrypsin film prepared by Guozhou et al is used for ammonia gas detection, and only 30nm band gap red shift is realized. In addition, they prepared PEDOT and polyacrylamide hydrogel composite films for glucose detection, where shrinkage of the hydrogel based on changes in glucose concentration caused a blue shift of the band gap of about 170nm, and PEDOT merely served as a conductive medium.
However, photonic crystals lacking large band gap modulation and having good environmental stability.
Disclosure of Invention
In view of the above problems, it is a first object of the present invention to provide a photonic crystal material having a large band gap modulation effect and stability in an organic environment, which has a large band gap modulation effect and can be stably stored in an organic solvent for a long period of time.
The second purpose of the invention is to provide a preparation method of the photonic crystal material with large band gap modulation effect and organic environment stability.
The third purpose of the invention is to provide a band gap modulation method of the photonic crystal material with large band gap modulation effect and organic environment stability.
The fourth purpose of the invention is to provide the application of the photonic crystal material with large band gap modulation effect and organic environment stability in the aspect of complex organic environment detection.
In order to achieve the first purpose, the invention adopts the following technical scheme:
the photonic crystal material with the large band gap modulation effect and the organic environment stability is characterized in that the photonic crystal material is a PEDOT photonic crystal with an inverse opal structure.
Further, the surface water contact angle of the photonic crystal material is larger than 150 degrees.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of a photonic crystal material with large band gap modulation effect and organic environment stability comprises the following steps:
providing a photonic crystal template;
providing an electrochemical polymerization reaction liquid containing a reaction monomer EDOT;
providing an electropolymerization reaction device, wherein the photonic crystal template treated by plasma is taken as a working electrode;
applying voltage to the electropolymerization reaction device to perform electrochemical polymerization on the electrochemical polymerization reaction liquid to obtain PEDOT photonic crystals on the photonic crystal template;
and washing, drying and removing the photonic crystal template to obtain the photonic crystal material.
Further, the photonic crystal template comprises a substrate and polystyrene microspheres periodically arranged on the substrate.
Further, the particle size of the polystyrene microsphere is 200-300 nm.
Furthermore, the polystyrene microsphere has a core-shell structure, wherein polystyrene is used as a core, and poly (acrylic acid-methyl methacrylate) is used as a shell.
Further, the preparation of the photonic crystal template comprises the following steps:
and (3) self-assembling polystyrene microspheres on a substrate to form a film by adopting a vertical deposition method to obtain the photonic crystal template.
Further, the electrochemical polymerization reaction solution also comprises solvent deionized water and electrolyte; in the electrochemical polymerization reaction liquid, the concentration of a reaction monomer EDOT is 0.01-0.04mol/L, and the concentration of an electrolyte is 0.1-0.2 mol/L.
Further, the electrolyte is selected from one of sodium p-toluenesulfonate, lithium perchlorate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate and tetrabutylammonium hexafluorophosphate.
Further, the electric polymerization reaction device is built by adopting an electrochemical workstation three-electrode system; the electric polymerization reaction device takes a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode.
Further, the electrochemical polymerization is polymerization for 5-10min under the voltage of 0.8-1.2V; or
And carrying out cyclic scanning for 10-20 circles at-0.6-1.25V by cyclic voltammetry to carry out polymerization.
In order to achieve the third purpose, the invention adopts the following technical scheme:
a band gap modulation method of a photonic crystal material with large band gap modulation effect and organic environment stability comprises the following steps: mixing the photonic crystal material with an organic solvent.
Further, the organic solvent is selected from one of hexane, n-octane, toluene, xylene, dichloromethane, tetrahydrofuran, isopropanol, acetone, acetonitrile, dimethylformamide, methanol, and dimethyl sulfoxide.
The fourth purpose is achieved, and the invention adopts the following technical scheme:
the application of a photonic crystal material with large band gap modulation effect and organic environment stability in the aspect of complex organic environment detection.
The invention has the following beneficial effects:
in the photonic crystal material provided by the invention, the PEDOT photonic crystal thin films with the first and inverse opal structures are more ordered in nano-size arrangement, the three-dimensional porous structure further has an increased specific surface area, and has a stronger response signal to an organic solvent, and the band gap red shift of up to 200nm can be realized in the presence of a very small amount of the organic solvent; secondly, the inverse opal-structure PEDOT photonic crystal film provided by the invention has excellent solution stability, is insoluble and infusible to most of solvents, keeps the surface structure color and band gap of a sample unchanged after being soaked for about one week, and can be in a severe liquid environment for a long time, so that the inverse opal-structure PEDOT photonic crystal film can be used for detecting complex organic environments.
According to the preparation method provided by the invention, the prepared PEDOT photonic crystal film with the inverse opal structure can realize the regulation and control of the super-hydrophobicity while removing the small spherical template by soaking in tetrahydrofuran, and the super-hydrophobicity can be stably maintained for a long time at room temperature. In addition, the preparation method is simple to operate, low in cost and suitable for large-scale preparation.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows the structural color and spectral changes of inverse opal-structured PEDOT photonic crystals prepared in example 16 of the present invention in response to toluene, dichloromethane, and dimethylsulfoxide.
Fig. 2 shows a summary of the bandgap red-shift amounts of the inverse opal-structured PEDOT photonic crystal prepared in example 17 of the present invention in response to various organic solvents.
Fig. 3 shows structural color and band gap changes of the inverse opal-structured PEDOT photonic crystal prepared in example 18 of the present invention before and after soaking in ethanol, tetrahydrofuran, and toluene for 48 hours.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
According to an embodiment of the invention, a photonic crystal material with large band gap modulation effect and organic environment stability is provided, and the photonic crystal material is a PEDOT photonic crystal with an inverse opal structure.
In the photonic crystal material provided by the invention, the PEDOT photonic crystal with the inverse opal structure has excellent solvent resistance in an organic solvent, and simultaneously has a strong response signal to the organic solvent, so that a large band gap is shown to move when responding to the organic solvent.
Further, the photonic crystal material is a film material.
Further, the photonic crystal material is super-hydrophobic in air, and the surface water contact angle is more than 150 degrees.
According to another embodiment of the present invention, there is provided a method for preparing a photonic crystal material having a large band gap modulation effect and stability in an organic environment, the method comprising the steps of:
providing a photonic crystal template;
providing an electrochemical polymerization reaction liquid containing a reaction monomer EDOT;
providing an electropolymerization reaction device, wherein the photonic crystal template treated by plasma is taken as a working electrode;
applying voltage to the electropolymerization reaction device to perform electrochemical polymerization on the electrochemical polymerization reaction liquid to obtain PEDOT photonic crystals on the photonic crystal template;
and washing, drying and removing the photonic crystal template to obtain the photonic crystal material.
Illustratively, in the above preparation method, the photonic crystal template comprises a substrate, and polystyrene microspheres periodically arranged on the substrate. Preferred substrates may be superhydrophilic solid substrates. Suitable superhydrophilic solid substrates include, but are not limited to, substrates selected from the group consisting of ordinary glass, conductive glass, quartz wafers, silicon wafers, and the like. In the method, the super-hydrophilic solid base material is utilized, and the polystyrene microspheres are assembled into the high-quality photonic crystal film on the surface of the polystyrene microspheres. Thereby being beneficial to preparing the PEDOT photonic crystal with the inverse opal structure and more uniform and stable structure.
Illustratively, the photonic crystal template is obtained by a method of self-assembling polystyrene microspheres into a film on a substrate by adopting a vertical deposition method. Specifically, the substrate can be placed in polystyrene microsphere emulsion and assembled into a photonic crystal template in a constant temperature and humidity chamber by a vertical deposition method. Still further, the vertical deposition comprises the steps of: diluting the polystyrene microsphere emulsion to be in a semitransparent state by adding water, vertically placing the substrate in the polystyrene microsphere emulsion, keeping the temperature at 20-80 ℃ and the humidity at 20-80% until the emulsion is completely evaporated, and self-assembling the polystyrene microspheres into the photonic crystal film on the surface of the substrate. The band gap of the photonic crystal film is about 500-750 nm.
Preferably, the polystyrene microsphere has a core-shell structure, wherein polystyrene is used as a core and poly (acrylic acid-methyl methacrylate) is used as a shell. The microspheres with the soft shell and the hard core are more beneficial to the close packing of the small balls in the assembling process, and a photonic crystal film with better quality is formed. Otherwise, the photonic crystal film is not tightly arranged, thereby affecting the quality of the PEDOT photonic crystal film of the inverse opal structure.
The exemplary polystyrene microsphere is prepared by an emulsion polymerization method, and specifically comprises the following steps:
adding 0.8-1.2 parts by mass of methyl methacrylate, 0.8-1.2 parts by mass of acrylic acid and 17-21 parts by mass of styrene into 80-100 parts by volume of water, and then adding 0-0.004 part by mass of emulsifier sodium dodecyl benzene sulfonate (the concentration of the emulsifier is lower than the critical micelle concentration) and 0.5-0.55 part by mass of buffer sodium bicarbonate to obtain a reaction solution; keeping the reaction liquid at 60-80 ℃ for 0.5-2h, then adding 0.45-0.5 part by mass of ammonium persulfate aqueous solution, and reacting at 70-90 ℃ for 10-15h under the condition of continuous stirring to obtain the polystyrene microsphere with the core-shell structure.
Illustratively, the particle size of the polystyrene microsphere is 200-300 nm. The polystyrene microspheres with the particle size range can be assembled into photonic crystal films with different band gaps, so that the inverse opal-structure PEDOT photonic crystals with different band gaps can be prepared. The particle size of the microspheres is too large or too small, so that the assembly is difficult and the band gap of the assembled photonic crystal film is not appropriate.
Further, the electrochemical polymerization reaction solution also comprises solvent deionized water and electrolyte; in the electrochemical polymerization reaction liquid, the concentration of a reaction monomer EDOT is 0.01-0.04mol/L, and the concentration of an electrolyte is 0.1-0.2 mol/L. Wherein the electrolyte is selected from one of sodium p-toluenesulfonate, lithium perchlorate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and tetrabutylammonium hexafluorophosphate.
Because the solubility of EDOT in deionized water is small, the electrochemical polymerization reaction solution needs to be uniformly stirred for 0.5-1h in the preparation process. So that the monomers and the electrolyte are fully dispersed in a solvent system to ensure the formation of the inverse opal-structured PEDOT photonic crystal in the subsequent reaction.
Preferably, the electropolymerization reaction device is built by adopting an electrochemical workstation three-electrode system; the electric polymerization reaction device takes a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode. The platinum sheet electrode is polished and cleaned before use, and the saturated calomel electrode is cleaned by deionized water to remove surface impurities before use. Compared with a chemical oxidation polymerization mode, the electro-polymerization can directly obtain the PEDOT photonic crystal film with higher purity on the surface of the working electrode, the electro-polymerization rate is controllable, uniform deposition is ensured by controlling experimental conditions, and the PEDOT photonic crystal film with the inverse opal structure and uniform and bright color is obtained.
Preferably, in the electropolymerization reaction device, the three electrodes are positioned at the same height in the reaction solution, and a platinum sheet electrode (with the size of 1cm x 2cm) is equivalent to the size of the working electrode of the photonic crystal template and is arranged in a face-to-face mode, and PEDOT is uniformly filled in the photonic crystal template.
Illustratively, the electrochemical polymerization is polymerization at a constant potential voltage of 0.8-1.2V for 5-10 min. When the voltage is lower than 0.8V, the EDOT monomer is difficult to induce to polymerize, and when the voltage is higher than 1.2V, the sample is easy to be oxidized to appear black. The polymerization reaction time is short, the filling amount of PEDOT in the photonic crystal template is small, the subsequent solvent detection is not facilitated, the polymerization time is too long, the PEDOT is excessively filled and is difficult to dissolve when the template pellet is subsequently removed, and the sample cannot present the structural color of the photonic crystal due to the coverage of the intrinsic color of the PEDOT film.
Or
The electrochemical polymerization is carried out by circularly scanning for 10-20 circles at-0.6-1.25V by cyclic voltammetry, and monomer EDOT in the induction reaction solution is polymerized into conductive polymer PEDOT under the doping of electrolyte; and the PEDOT is gradually deposited from one side of the substrate (if the conductive glass is used, the conductive side of the substrate) to the outer side of the photonic crystal template and is filled into the small template ball gap, so that the composite sample combining the polystyrene microsphere and the PEDOT can be prepared. In the cyclic voltammetry, the voltage is lower than-0.6V, the counter electrode (platinum sheet electrode) is easy to oxidize, blacken and soften, and the voltage is higher than 1.25V, so that the sample is easy to be oxidized and blackened. The cycle is less than 10 circles, the filling amount of PEDOT in the photonic crystal template is small, the subsequent solvent detection is not facilitated, the cycle is more than 20 circles, the PEDOT is excessively filled and is still difficult to dissolve when the template beads are removed later, and the sample cannot present the structural color of the photonic crystal due to the coverage of the intrinsic color of the PEDOT film.
Further, the water washing mainly washes away oligomers and impurities on the surface of the sample. Wherein, the oligomer is mainly dimer or trimer and other oligomers with smaller molecular weight, and the impurities are mainly unreacted monomers and electrolytes adsorbed on the surface of the sample.
Further, the method for removing the photonic crystal template is mainly removing by soaking in tetrahydrofuran.
According to another embodiment of the present invention, there is provided a bandgap modulation method for a photonic crystal material having a large bandgap modulation effect and stability in an organic environment, the method comprising the steps of: mixing the photonic crystal material with an organic solvent. Preferably, an organic solvent is dripped on the surface of the photonic crystal material. In the method, the band gap red shift of up to 180-250nm can be realized. That is, the photonic crystal material has a strong response signal to the presence of an organic solvent.
Illustratively, the organic solvent is selected from one of hexane, n-octane, toluene, xylene, dichloromethane, tetrahydrofuran, isopropanol, acetone, acetonitrile, dimethylformamide, methanol, and dimethylsulfoxide.
Further, the photonic crystal material is soaked in an organic solvent for 144h for a long time, and after the organic solvent is evaporated to be dry, the structural color and the band gap of a sample are not obviously changed. The organic solvent is selected from one of hexane, n-octane, toluene, xylene, dichloromethane, tetrahydrofuran, isopropanol, acetone, acetonitrile, dimethylformamide, methanol and dimethyl sulfoxide. Namely, the photonic crystal material has good stability in organic solvents.
The invention further provides the application of the photonic crystal material with large band gap modulation effect and organic environment stability in the aspect of complex organic environment detection.
The PEDOT photonic crystal with the inverse opal structure has excellent solvent resistance in an organic solvent, and has a strong response signal to the organic solvent, so that the environment can be reflected by the fact that the PEDOT photonic crystal with the inverse opal structure presents large band gap moving behavior when responding to the organic solvent.
The photonic crystal material provided by the invention has the following advantages:
1. the invention further enhances the response of the surface of the PEDOT photonic crystal film with the inverse opal structure to an organic solvent by introducing the photonic crystal structure into the PEDOT film with the super-oleophylic property. Specifically, the color change and band gap movement of the PEDOT photonic crystal film structure can be monitored in real time by combining an optical microscope and a fiber spectrometer. Firstly, a certain area is positioned by adopting a fiber spectrometer, and the initial band gap and the structural color of a sample are collected. When the organic solvent is dripped on the surface of the PEDOT photonic crystal film, the band gap red shift of 200nm as high as both the structural color and the band gap appears immediately (within 1 s), which is not shown in the prior anti-protein structural material, and the initial state is recovered after the solvent is volatilized to be dried. And the structural color and the band gap shift degree of the PEDOT photonic crystal film are related to the selected organic solvent type. A green inverse opal-structured PEDOT photonic crystal film (with a band gap of 536nm) is selected as a starting sample, 2uL of toluene is dripped on the surface of the film, the band gap of the sample is red-shifted by 226nm, and the sample reaches a near infrared region (with a band gap of 762nm) which can not be observed by naked eyes. Similarly, 2uL of methylene chloride was dropped onto the surface of the film, and the band gap of the sample was red-shifted by 210nm to reach a near infrared region (band gap of 746nm) that was not observed with the naked eye. 2uL of dimethyl sulfoxide is dripped on the surface of the membrane, the band gap of the sample is red-shifted to 234nm, and the sample reaches a near infrared region (the band gap is 770nm) which can not be observed by naked eyes. The method expands the large band gap red shift behavior of most organic solvents, and further proves that the inverse opal PEDOT photonic crystal film has faster and stronger response characteristics to the organic solvents. The traditional photonic crystal material with the inverse opal structure does not have such rapid and obvious organic solvent response, so that the invention provides the PEDOT photonic crystal film with the inverse opal structure and the large band gap modulation effect, and the application in different complex organic environments is greatly expanded.
Stable property of PEDOT photonic crystal film in organic environment
The prepared inverse opal-structured PEDOT photonic crystal has excellent solution stability, is insoluble and infusible to most solvents, and can be in a severe liquid environment for a long time. Specifically, a specific PEDOT photonic crystal film is selected, and structural color and spectral change of the surface of the photonic crystal film are observed through an optical microscope and a fiber spectrometer. And soaking the PEDOT photonic crystal film with the inverse opal structure into various organic solvents, and keeping the structure color and the band gap of the PEDOT photonic crystal unchanged after the sample is taken out and volatilized to be dry. The PEDOT photonic crystal film with the green inverse opal structure (with the band gap of 510nm) is soaked in the ethanol solvent for 48 hours, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (512nm) of the surface of the sample are not obviously changed. Similarly, a PEDOT photonic crystal film with a green inverse opal structure (with a band gap of 535nm) is soaked in a tetrahydrofuran solvent for 48h, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (533nm) of the surface of a sample are not obviously changed. The PEDOT photonic crystal film with the green inverse opal structure (with the band gap of 523nm) is soaked in a toluene solvent for 48 hours, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (520nm) of the surface of a sample are not obviously changed. The method expands the types of organic solvents, and the phenomenon still exists, so that the excellent stability of the inverse opal-structured PEDOT photonic crystal film in an organic environment is proved.
The technical solution of the present invention is described below with reference to some specific examples:
example 1
1. Preparation of core-shell structure polystyrene microsphere
Adding 0.8 mass part of methyl methacrylate, 0.8 mass part of acrylic acid and 17 mass parts of styrene into 80 mass parts of water, and then adding 0 mass part of emulsifier sodium dodecyl benzene sulfonate and 0.5 mass part of buffer sodium bicarbonate to obtain a reaction solution; and (3) keeping the reaction liquid at 60 ℃ for 0.5h, then adding 0.45 part by mass of ammonium persulfate aqueous solution, and reacting at 70 ℃ for 10h under the condition of continuous stirring to obtain the polystyrene microsphere with the core-shell structure.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 80 ℃, the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 0.5 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 30s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 2
1. Preparation of core-shell structure polystyrene microsphere
Adding 1 part by mass of methyl methacrylate, 1 part by mass of acrylic acid and 17 parts by mass of styrene into 90 parts by mass of water, and then adding 0.002 part by mass of emulsifier sodium dodecyl benzene sulfonate and 0.52 part by mass of buffer sodium bicarbonate to obtain a reaction solution; and (3) keeping the reaction liquid at 70 ℃ for 1h, then adding 0.48 part by mass of ammonium persulfate aqueous solution, and reacting at 80 ℃ for 12h under the condition of continuous stirring to obtain the polystyrene microsphere with the core-shell structure.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 20 ℃, the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 3
1. Preparation of core-shell structure polystyrene microsphere
Adding 1.2 parts by mass of methyl methacrylate, 1.2 parts by mass of acrylic acid and 21 parts by mass of styrene into 100 parts by mass of water, and then adding 0.004 part by mass of emulsifier sodium dodecyl benzene sulfonate and 0.55 part by mass of buffer sodium bicarbonate to obtain a reaction solution; and (3) keeping the reaction liquid at 80 ℃ for 2h, then adding 0.5 part by mass of ammonium persulfate aqueous solution, and reacting at 90 ℃ for 15h under the condition of continuous stirring to obtain the polystyrene microsphere with the core-shell structure.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 50 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal film with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.2 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 100s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 4
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 20 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.2 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 150s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 8min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 5
1. Preparation of core-shell polystyrene microspheres as in example 2
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 50%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.01 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 8min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 6
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 80%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.03 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device for electropolymerization for 10min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 7
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.04 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 0.8V to the reaction device for electropolymerization for 10min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 8
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 0.8V to the reaction device, and performing electropolymerization for 12min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 9
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 250nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 60%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 625 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (625nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 0.8V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (480-.
Example 10
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 200nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 60%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 500 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (500nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.2V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (380-450 nm).
Example 11
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (625nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.2V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (480-.
Example 12
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.2V to the reaction device, and performing electropolymerization for 10min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 13
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) circularly scanning for 10 circles between-0.6 and 1.25V by cyclic voltammetry to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 14
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) circularly scanning for 15 circles between-0.6 and 1.25V by cyclic voltammetry to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 15
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) circularly scanning for 20 circles between-0.6 and 1.25V by cyclic voltammetry to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
Example 16
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
4. Large band gap modulation in response to organic solvents
And an optical microscope and a fiber spectrometer are used together to monitor the color change and band gap movement of the PEDOT photonic crystal film structure in real time. A green inverse opal-structured PEDOT photonic crystal film (with a band gap of 536nm) is selected as a starting sample to be tested, 2uL of toluene is dripped on the surface of the film, the band gap of the sample is red-shifted by 226nm, and the sample reaches a near infrared region (with a band gap of 762nm) which can not be observed by naked eyes. Similarly, 2uL of methylene chloride was dropped onto the surface of the film, and the band gap of the sample was red-shifted by 210nm to reach a near infrared region (band gap of 746nm) that was not observed with the naked eye. 2uL of dimethyl sulfoxide is dripped on the surface of the membrane, the band gap of the sample is red-shifted to 234nm, and the sample reaches a near infrared region (the band gap is 770nm) which can not be observed by naked eyes. The structural color and spectral changes of the inverse opal PEDOT photonic crystal in response to toluene, dichloromethane and dimethylsulfoxide are shown in fig. 1.
Example 17
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
4. Large band gap modulation in response to organic solvents
And an optical microscope and a fiber spectrometer are used together to monitor the color change and band gap movement of the PEDOT photonic crystal film structure in real time. A green inverse opal-structured PEDOT photonic crystal film (with a band gap of 536nm) is selected as a starting sample to be tested, the average value of the results of three experiments is used for drawing, and the measurement error range is marked. Various organic solvents are dropped on the surface of the film and the band gap red shift amount is collected, for example, hexane (164 +/-10 nm), n-octane (173.4 +/-20 nm), toluene (226 +/-25 nm), xylene (210 +/-18 nm), dichloromethane (210 +/-12 nm), tetrahydrofuran (183 +/-13 nm), isopropanol (178 +/-16 nm), ethanol (188 +/-10 nm), acetone (184 +/-8 nm), acetonitrile (174 +/-20 nm), dimethylformamide (213 +/-29 nm), methanol (171 +/-18 nm), dimethyl sulfoxide (234 +/-30 nm) and the like, and the result shows that the inverse opal structure PEDOT photonic crystal film has large band gap red shift behavior to most of the organic solvents, and the band gap red shift amount is summarized as shown in FIG. 2.
Example 18
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
4. Stability test of inverse opal-structured PEDOT photonic crystals in organic solvents
And observing the structural color and the spectral change of the surface of the photonic crystal film through an optical microscope and a fiber spectrometer. The PEDOT photonic crystal film with the green inverse opal structure (with the band gap of 510nm) is soaked in the ethanol solvent for 48 hours, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (512nm) of the surface of the sample are not obviously changed. Similarly, a PEDOT photonic crystal film with a green inverse opal structure (with a band gap of 535nm) is soaked in a tetrahydrofuran solvent for 48h, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (533nm) of the surface of a sample are not obviously changed. The PEDOT photonic crystal film with the green inverse opal structure (with the band gap of 523nm) is soaked in a toluene solvent for 48 hours, and after the solvent is volatilized to be dried, the structural color (green) and the band gap (520nm) of the surface of a sample are not obviously changed. After continuing the immersion in toluene for 144h and the solvent evaporating off, the structural color (green) and band gap (519nm) of the sample surface remained unchanged. The structural color and band gap change of the inverse opal-structured PEDOT photonic crystal before and after being soaked in ethanol, tetrahydrofuran and toluene for 48 hours is shown in fig. 3.
Example 19
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 300nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃ and the humidity is 60 percent), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 750 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (750nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (510-575 nm).
4. Super-hydrophobicity of PEDOT photonic crystal film with inverse opal structure in air
The contact angle change of the water drop on the inverse opal-structured PEDOT film was observed with a contact angle meter. And selecting a green inverse opal-structured PEDOT photonic crystal film obtained after being soaked in tetrahydrofuran for 24 hours for testing, dripping 1uL of water on the surface of the film, and performing numerical measurement. 5 sets of samples were tested and 5 different positions were chosen for each sample. The contact angle value of water drops on the surface of the PEDOT photonic crystal film is larger than 150 degrees, and the water drops can easily slide on the surface of the film.
Example 20
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 250nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 60%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 625 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (625nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (480-.
4. Large band gap modulation in response to organic solvents
And an optical microscope and a fiber spectrometer are used together to monitor the color change and band gap movement of the PEDOT photonic crystal film structure in real time. A blue inverse opal-structured PEDOT photonic crystal film (band gap of 480nm) is selected as a starting sample to be tested, various organic solvents are dropped on the surface of the film, and band gap red shift amounts are collected, such as hexane (172 + -12 nm), n-octane (179 + -18 nm), toluene (220 + -20 nm), xylene (215 + -16 nm), dichloromethane (202 + -14 nm), tetrahydrofuran (190 + -16 nm), isopropanol (175 + -14 nm), acetone (180 + -10 nm), acetonitrile (178 + -18 nm), dimethylformamide (223 + -20 nm), methanol (173 + -18 nm), dimethylsulfoxide (238 + -20 nm), and the like. The PEDOT photonic crystal film has large band gap red-shift behavior to most organic solvents, and the blue color is red-shifted to a red visible region.
Example 21
1. The preparation of the polystyrene microspheres with core-shell structures is the same as that in example 2.
2. Preparation of photonic crystal template
Pouring the polystyrene microsphere emulsion with the particle size of 200nm into a small beaker, vertically placing the super-hydrophilic solid substrate into the small beaker filled with the polystyrene emulsion with a certain concentration, placing the small beaker in a constant temperature and humidity box (the temperature is 60 ℃, the humidity is 60%), and completely evaporating and drying the emulsion to obtain the photonic crystal template with the band gap of about 500 nm.
3. Preparation of inverse opal-structure PEDOT photonic crystal
(1) Preparing electrochemical polymerization reaction liquid and uniformly stirring for 1 h; the solvent of the reaction solution is deionized water; the concentration of the reaction monomer EDOT is 0.02 mol/L; the concentration of the electrolyte to the sodium toluenesulfonate is 0.1 mol/L;
(2) an electrochemical workstation three-electrode system is adopted to build an electric polymerization reaction device; the device takes a platinum sheet electrode (with the size of 1cm x 2cm) as a counter electrode, a saturated calomel electrode as a reference electrode, and a photonic crystal template (500nm) as a working electrode after being treated for 60s by a plasma technology;
(3) applying a voltage of 1.0V to the reaction device, and performing electropolymerization for 6min to obtain a composite sample combining the polystyrene microspheres and the PEDOT;
(4) washing the oligomer and the impurities on the surface of the composite sample by using deionized water and airing;
(5) and soaking the composite sample in tetrahydrofuran to dissolve the photonic crystal template to obtain the PEDOT photonic crystal with the inverse opal structure with different band gaps (380-450 nm).
4. Large band gap modulation in response to organic solvents
And an optical microscope and a fiber spectrometer are used together to monitor the color change and band gap movement of the PEDOT photonic crystal film structure in real time. A PEDOT photonic crystal film with an inverse opal structure in an ultraviolet region (with a band gap of 380nm) is selected as a starting sample to be tested, various organic solvents are dropped on the surface of the film, and band gap red shift amounts are collected, such as hexane (175 +/-12 nm), n-octane (182 +/-14 nm), toluene (212 +/-14 nm), xylene (210 +/-12 nm), dichloromethane (208 +/-14 nm), tetrahydrofuran (192 +/-18 nm), isopropanol (176 +/-16 nm), acetone (181 +/-12 nm), acetonitrile (176 +/-16 nm), dimethylformamide (225 +/-24 nm), methanol (220 +/-18 nm), dimethyl sulfoxide (234 +/-20 nm) and the like. The PEDOT photonic crystal film has large band gap red-shift behavior to most of organic solvents, and is red-shifted from an ultraviolet region to a green visible region.
Comparative example 1
The photonic crystal material in example 1 was replaced with "a photonic crystal material having a carbon dot photonic crystal of an inverse opal structure", and the maximum band gap shift amount thereof was measured to be 100 nm.
Comparative example 2
Example 1 was repeated except that the preparation method was changed to preparation by template sacrifice and in-situ chemical oxidative polymerization during the "preparation of PEDOT photonic crystals".
The prepared photonic crystal material has response characteristics in a glucose solution, and the blue shift of the band gap of the film caused by contraction based on the concentration change of the glucose solution is about 170 nm.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The photonic crystal material with the large band gap modulation effect and the organic environment stability is characterized in that the photonic crystal material is a PEDOT photonic crystal with an inverse opal structure.
2. The photonic crystal material of claim 1, wherein the photonic crystal material has a surface water contact angle greater than 150 °.
3. The method of preparing a photonic crystal material according to claim 1, comprising the steps of:
providing a photonic crystal template;
providing an electrochemical polymerization reaction liquid containing a reaction monomer EDOT;
providing an electropolymerization reaction device, wherein the photonic crystal template treated by plasma is taken as a working electrode;
applying voltage to the electropolymerization reaction device to perform electrochemical polymerization on the electrochemical polymerization reaction liquid to obtain PEDOT photonic crystals on the photonic crystal template;
and washing, drying and removing the photonic crystal template to obtain the photonic crystal material.
4. The method of claim 3, wherein the photonic crystal template comprises a substrate, and polystyrene microspheres periodically arranged on the substrate;
preferably, the particle size of the polystyrene microsphere is 200-300 nm;
preferably, the polystyrene microsphere has a core-shell structure, wherein polystyrene is used as a core and poly (acrylic acid-methyl methacrylate) is used as a shell.
5. The method of claim 4, wherein the preparation of the photonic crystal template comprises the steps of:
and (3) self-assembling polystyrene microspheres on a substrate to form a film by adopting a vertical deposition method to obtain the photonic crystal template.
6. The preparation method according to claim 3, wherein the electrochemical polymerization reaction solution further comprises deionized water as a solvent and an electrolyte; in the electrochemical polymerization reaction liquid, the concentration of a reaction monomer EDOT is 0.01-0.04mol/L, and the concentration of an electrolyte is 0.1-0.2 mol/L; preferably, the electrolyte is selected from one of sodium p-toluenesulfonate, lithium perchlorate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate and tetrabutylammonium hexafluorophosphate;
preferably, the electropolymerization reaction device is built by adopting an electrochemical workstation three-electrode system; the electric polymerization reaction device takes a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode.
7. The method according to claim 3, wherein the electrochemical polymerization is polymerization at a voltage of 0.8 to 1.2V for 5 to 10 min; or
And carrying out cyclic scanning for 10-20 circles at-0.6-1.25V by cyclic voltammetry to carry out polymerization.
8. The method of claim 1, comprising the steps of: mixing the photonic crystal material with an organic solvent.
9. The method according to claim 8, wherein the organic solvent is selected from one of hexane, n-octane, toluene, xylene, dichloromethane, tetrahydrofuran, isopropanol, acetone, acetonitrile, dimethylformamide, methanol, and dimethylsulfoxide.
10. The use of the photonic crystal material with large band gap modulation effect and organic environment stability of claim 1 in complex organic environment detection.
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| CN117626534A (en) * | 2024-01-26 | 2024-03-01 | 东华大学 | Solvent response color-changing piezoelectric material and preparation method and application thereof |
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