CN107602890B - Preparation method of cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film - Google Patents
Preparation method of cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film Download PDFInfo
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- XURWEOGGSNPGHZ-UHFFFAOYSA-N [Ti]O[Ce] Chemical compound [Ti]O[Ce] XURWEOGGSNPGHZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 117
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 13
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 239000007921 spray Substances 0.000 claims abstract description 4
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 22
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 18
- -1 polytetrafluoroethylene Polymers 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- GZRQIDVFTAQASP-UHFFFAOYSA-N [Ce+3].[O-2].[Ti+4] Chemical compound [Ce+3].[O-2].[Ti+4] GZRQIDVFTAQASP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite film and application thereof. The composite film is prepared by the following method: adding 3, 4-ethylenedioxythiophene and cerium-titanium-oxygen clusters prepared by a hydrothermal synthesis method into a container filled with acetonitrile and dichloromethane in advance, sealing the container by using a rubber head, injecting a mixed solution of acetonitrile and dichloromethane in which iron p-toluenesulfonate is dissolved into the container under magnetic stirring, and stirring for reacting for 6-10 hours to obtain a polymerization solution; and pouring the polymerization solution into a spray gun, taking clean ITO glass, and spraying the clean ITO glass on a conductive surface of the ITO glass to obtain the cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film. The prepared composite film can be used as an electrochromic material to be applied to the fields of intelligent windows and the like.
Description
Technical Field
The invention relates to a novel film, in particular to a cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene (Ce @ TiO) composite film2PEDOT) film, and a preparation method and application thereof.
Background
Electrochromic is a new research field, and has the following advantages: the suitable working temperature range is large; the energy consumption is low, and the matching with an integrated circuit is easy; the color adjustable range is wide and continuous color change can be realized; has memory function, and the color change can be maintained in open circuit state.
The cerium-titanium-oxygen cluster belongs to a multi-metal-oxygen cluster, and rare earth metal elements and transition metal elements in the structure of the cerium-titanium-oxygen cluster are filled in the vacancy of anions of the cerium-titanium-oxygen cluster. The structure of the organic polar solvent can not be changed after being dissolved, and particularly for the organic polar solvent, the application range of the organic polar solvent is wider due to the characteristic that the structure of the organic polar solvent can not be changed. The polymetal oxygen cluster has excellent photoelectric property, electrochemical property and electrochromic property, and the electrochromic mechanism is that when a sufficient voltage is applied, electrons are injected on the empty track of metal ions, the metal ions are changed from a high valence state to a low valence state, and the color is changed; when the applied voltage is changed, the metal ions lose electrons, the metal ions return to a high valence state from a low valence state, and the color is restored to the original color.
3, 4-Ethylenedioxythiophene (EDOT) is used as a common conductive polymer monomer, and a Polymer (PEDOT) of the EDOT has the characteristics of high conductivity, good stability, high contrast, high response speed, high visible light transmittance and the like, so that the EDOT becomes a hotspot in the field of electrochromic research.
Disclosure of Invention
The invention aims to provide a simple method for preparing a cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film with excellent photoelectric properties.
The invention adopts the following technical scheme for solving the technical problems:
a cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite film is prepared by the following steps:
(1) preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding tetraethyl titanate, anhydrous cerium chloride and anhydrous ethanol into an inner container coated with polytetrafluoroethylene on the surface, then putting the inner container into a hydrothermal reaction kettle, reacting at the temperature of 100-200 ℃ for 48-96 hours, taking the inner container out of the reaction kettle, cooling to room temperature to obtain an orange-red solution, taking the orange-red solution out of the inner container, standing at room temperature to slowly volatilize a solvent, and obtaining a red crystal after 30-60 days, namely the cerium-titanium-oxygen cluster; the volume ratio of the tetraethyl titanate to the absolute ethyl alcohol is 1: 1-4; the amount of the anhydrous cerium chloride substance is 0.05-0.15 mmol/mL based on the volume of the tetraethyl titanate;
(2)Ce@TiO2chemical polymerization of PEDOT: adding 3, 4-ethylenedioxythiophene and the cerium-titanium-oxygen cluster prepared in the step (1) into a container filled with acetonitrile and dichloromethane in advance to obtain a primarySealing the container, injecting a mixed solution of acetonitrile dissolved with ferric p-toluenesulfonate and dichloromethane into the container under magnetic stirring, and stirring for reaction for 6-10 h to obtain a polymerization solution;
(3)Ce@TiO2preparation of PEDOT films: and (3) pouring the polymerization solution obtained in the step (2) into a spray gun, taking clean ITO glass, and spraying the clean ITO glass on a conductive surface of the ITO glass to obtain the cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film.
Further, the mass ratio of the 3, 4-ethylenedioxythiophene to the cerium-titanium-oxygen cluster in the step (2) is 1-2: 1, and preferably 1: 1.
Further, in the step (2), the volume ratio of acetonitrile to dichloromethane in the container filled with acetonitrile and dichloromethane in advance is 1-2: 1, preferably 1: 1.
Furthermore, in the step (2), the total volume of the acetonitrile and the dichloromethane which are filled in advance is 80-120 mL/g, preferably 110mL/g based on the mass of the 3, 4-ethylenedioxythiophene.
Further, in the mixed solution of acetonitrile and dichloromethane in which iron p-toluenesulfonate is dissolved in the step (2), iron p-toluenesulfonate is used as a solute, the concentration is 0.01 to 0.02g/mL, preferably 0.01g/mL, acetonitrile and dichloromethane are used as solvents, and the volume ratio of the acetonitrile to the dichloromethane is 1 to 2:1, preferably 1: 1.
Further, the volume ratio of the mixed solution to the initial solution in the step (2) is 1-2: 1, preferably 1: 1.
Further, the speed of injecting the mixed solution into the container in the step (2) is 1-5 mL/min, preferably 2.5 mL/min.
Further, the stirring reaction time in the step (2) is 6-10 hours, and 8 hours is preferred.
Further, the invention provides an application of the cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite film as an electrochromic material.
The surface appearance of the composite film is represented by a Scanning Electron Microscope (SEM), the photophysical property of the composite film is represented by an ultraviolet-visible light absorption spectrum, and the electrochromism and stability of the composite film are represented by an electrochemical workstation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method is simple and easy to implement, and does not need harsh conditions.
(2) The spraying and electrochemical polymerization method can make the obtained composite film uniform and stable.
(3) The prepared composite film has excellent electrochromic performance and can be used in the fields of intelligent windows and the like.
Drawings
FIG. 1 is an SEM photograph of a composite film obtained in example 1.
FIG. 2 is a graph showing the UV absorption of the composite film obtained in example 1.
FIG. 3 is a graph showing the contrast of the composite film obtained in example 1.
FIG. 4 is a graph of the cycling stability of the composite film made in example 1.
FIG. 5 is a graph of the electrochromic color of the composite film prepared in example 1 at-1V.
FIG. 6 is a graph of electrochromic color of the composite film prepared in example 1 at a voltage of 2V.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding 3.5ml of tetraethyl titanate, 1mmol (0.246g) of anhydrous cerium chloride and 7ml of anhydrous ethanol into an inner container of polytetrafluoroethylene, then putting the inner container into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to react for three days at 150 ℃, and then taking out the reaction kettle to cool to room temperature to obtain an orange-red solution. Taking the orange-red solution out of the liner, placing the orange-red solution in a sample bottle, standing the sample bottle at room temperature, slowly volatilizing the solvent, and obtaining red crystals, namely cerium-titanium-oxygen clusters after several months.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.5g EDOT,20ml dichloromethane, 0.55g cerium-titanium-oxygen cluster and rotor into a round bottom flask containing 20ml acetonitrile, sealing with rubber head, stirring, and injecting 50ml iron p-toluenesulfonate acetonitrile dichlorine into the flask at a speed of about 2.5ml/minA mixture solution of acetonitrile 25ml, dichloromethane 25ml and iron p-toluenesulfonate 1g was stirred and reacted for 8 hours.
(3)Ce@TiO2Preparation of PEDOT films: pouring the polymerization solution obtained in the step (2) into a spray gun, taking clean ITO glass, and spraying the clean ITO glass on a conductive surface of the ITO glass to obtain the Ce @ TiO2A PEDOT film.
SEM tests were performed on the composite film prepared in example 1, as shown in fig. 1, to demonstrate successful complexation of cerium-titanium-oxygen clusters with PEDOT.
The composite film prepared in example 1 was subjected to a uv test of a three-electrode system, as shown in fig. 2, which indicates that the composite film actually exhibits electrochromic phenomenon.
The composite film prepared in example 1 was subjected to a contrast test for a three-electrode system, as shown in fig. 3, which illustrates the higher color-changing contrast of the composite film.
The cyclic voltammetry stability test of the three-electrode system was performed on the composite film prepared in example 1, and fig. 4 shows that the composite film has a certain cyclic stability.
Three-electrode system: the working electrode is ITO glass loaded with a composite film, the counter electrode is a platinum electrode, the reference electrode is an Ag/AgCl electrode, and the electrolyte is 1mol/L dichloromethane solution of tetrabutylammonium hexafluorophosphate.
Example 2
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.5g EDOT,20ml dichloromethane, 0.56g cerium-titanium-oxygen cluster and rotor into a round bottom flask containing 20ml acetonitrile, sealing with a rubber head, starting stirring, injecting 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution into the flask at the speed of about 5ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 1g, and stirring and reacting for 8 hours.
(3) The procedure is as in example 1.
Example 3
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: to a round bottom flask containing 20ml acetonitrile was added 0.5g EDOT,20ml dichloroMethane, 0.56g cerium-titanium-oxide cluster and a rotor are sealed by a rubber head, stirring is started, 50ml of iron p-toluenesulfonate acetonitrile-dichloromethane mixed solution is injected into a flask at the speed of about 1ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 1g, and stirring reaction is carried out for 8 hours.
(3) The procedure is as in example 1.
Example 4
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: 0.5g EDOT,20ml dichloromethane, 0.56g cerium-titanium-oxygen cluster and rotor are added into a round bottom flask containing 20ml acetonitrile, after the rubber head is used for sealing, stirring is started, 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution is injected into the flask at the speed of about 2.5ml/min, wherein 25ml acetonitrile, 25ml dichloromethane and 1g iron p-toluenesulfonate are stirred and reacted for 6 hours.
(3) The procedure is as in example 1.
Example 5
(1) The procedure is as in example 1
(2)Ce@TiO2Chemical polymerization of PEDOT: 0.5g EDOT,20ml dichloromethane, 0.56g cerium-titanium-oxygen cluster and rotor are added into a round bottom flask containing 20ml acetonitrile, after the rubber head is used for sealing, stirring is started, 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution is injected into the flask at the speed of about 2.5ml/min, wherein 25ml acetonitrile, 25ml dichloromethane and 1g iron p-toluenesulfonate are stirred and reacted for 8 hours.
(3) The procedure is as in example 1.
Example 6
(1) Preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding 3.5ml of tetraethyl titanate, 1mmol of anhydrous cerium chloride and 14ml of anhydrous ethanol into an inner container of polytetrafluoroethylene, then putting the mixture into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to react for three days at 150 ℃, and then taking out the reaction kettle to cool to room temperature to obtain an orange-red solution. Taking the orange-red solution out of the liner, placing the orange-red solution in a sample bottle, standing the sample bottle at room temperature, slowly volatilizing the solvent, and obtaining red crystals, namely cerium-titanium-oxygen clusters after several months.
(2) The procedure is as in example 1
(3) The procedure is as in example 1
Example 7
(1) Preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding 3.5ml of tetraethyl titanate, 1mmol of anhydrous cerium chloride and 7ml of anhydrous ethanol into an inner container of polytetrafluoroethylene, then putting the mixture into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to react for three days at 100 ℃, and then taking out the reaction kettle to cool to room temperature to obtain an orange-red solution. Taking the orange-red solution out of the liner, placing the orange-red solution in a sample bottle, standing the sample bottle at room temperature, slowly volatilizing the solvent, and obtaining red crystals, namely cerium-titanium-oxygen clusters after several months.
(2) The procedure is as in example 1
(3) The procedure is as in example 1
Example 8
(1) Preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding 3.5ml of tetraethyl titanate, 1mmol of anhydrous cerium chloride and 7ml of anhydrous ethanol into an inner container of polytetrafluoroethylene, then putting the mixture into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into an oven to react for three days at 200 ℃, and then taking out the reaction kettle to cool to room temperature to obtain an orange-red solution. Taking the orange-red solution out of the liner, placing the orange-red solution in a sample bottle, standing the sample bottle at room temperature, slowly volatilizing the solvent, and obtaining red crystals, namely cerium-titanium-oxygen clusters after several months.
(2) The procedure is as in example 1
(3) The procedure is as in example 1
Example 9
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.3g of EDOT,20ml of dichloromethane, 0.3g of cerium-titanium-oxygen cluster and a rotor into a round-bottom flask containing 20ml of acetonitrile, sealing the round-bottom flask by using a rubber head, starting stirring, injecting 50ml of iron p-toluenesulfonate acetonitrile-dichloromethane mixed solution into the round-bottom flask at the speed of about 2.5ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 1g, and carrying out stirring reaction for 8 hours.
(3) The procedure is as in example 1.
Example 10
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.5g of EDOT,13ml of dichloromethane, 0.56g of cerium-titanium-oxygen cluster and a rotor into a round-bottom flask containing 26ml of acetonitrile, sealing the round-bottom flask by using a rubber head, starting stirring, injecting 50ml of iron p-toluenesulfonate acetonitrile-dichloromethane mixed solution into the round-bottom flask at the speed of about 2 and 5ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 1g, and carrying out stirring reaction for 8 hours.
(3) The procedure is as in example 1.
Example 11
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.5g EDOT,20ml dichloromethane, 0.25g cerium-titanium-oxygen cluster and rotor into a round bottom flask containing 20ml acetonitrile, sealing with a rubber head, starting stirring, injecting 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution into the flask at the speed of about 2.5ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 1g, and stirring and reacting for 8 hours.
(3) The procedure is as in example 1.
Example 12
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: 0.5g EDOT,20ml dichloromethane, 0.56g cerium-titanium-oxygen cluster and rotor are added into a round bottom flask containing 20ml acetonitrile, after the rubber head is used for sealing, stirring is started, 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution is injected into the flask at the speed of about 2.5ml/min, wherein 33ml acetonitrile, 17ml dichloromethane and 1g iron p-toluenesulfonate are stirred for reaction for 8 hours.
(3) The procedure is as in example 1.
Example 13
(1) The procedure is as in example 1.
(2)Ce@TiO2Chemical polymerization of PEDOT: adding 0.5g EDOT,20ml dichloromethane, 0.56g cerium-titanium-oxygen cluster and rotor into a round bottom flask containing 20ml acetonitrile, sealing with a rubber head, starting stirring, injecting 50ml iron p-toluenesulfonate acetonitrile dichloromethane mixed solution into the flask at the speed of about 2.5ml/min, wherein the acetonitrile is 25ml, the dichloromethane is 25ml, and the iron p-toluenesulfonate is 0.5g, stirring and reactingFor 8 hours.
(3) The procedure is as in example 1.
Example 14
(1) Preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding 7ml of tetraethyl titanate, 1mmol of anhydrous cerium chloride and 7ml of anhydrous ethanol into an inner container of polytetrafluoroethylene, then putting the inner container into a hydrothermal reaction kettle, putting the reaction kettle into an oven to react for three days at 150 ℃, and then taking out the reaction kettle to cool to room temperature to obtain an orange-red solution. Taking the orange-red solution out of the liner, placing the orange-red solution in a sample bottle, standing the sample bottle at room temperature, slowly volatilizing the solvent, and obtaining red crystals, namely cerium-titanium-oxygen clusters after several months.
(2) The procedure is as in example 1
(3) The procedure is as in example 1.
Claims (9)
1. The cerium-titanium-oxygen cluster/poly 3, 4-ethylene dioxythiophene composite film is characterized in that the preparation method of the composite film comprises the following steps:
(1) preparing cerium-titanium-oxygen cluster by using a hydrothermal synthesis method: adding tetraethyl titanate, anhydrous cerium chloride and anhydrous ethanol into an inner container coated with polytetrafluoroethylene on the surface, then putting the inner container into a hydrothermal reaction kettle, reacting at the temperature of 100-200 ℃ for 48-96 hours, taking the inner container out of the reaction kettle, cooling to room temperature to obtain an orange-red solution, taking the orange-red solution out of the inner container, standing at room temperature to slowly volatilize a solvent, and obtaining a red crystal after 30-60 days, namely the cerium-titanium-oxygen cluster; the volume ratio of the tetraethyl titanate to the absolute ethyl alcohol is 1: 1-4; the amount of the anhydrous cerium chloride substance is 0.142-0.285 mmol/mL in terms of the volume of tetraethyl titanate;
(2)Ce@TiO2chemical polymerization of PEDOT: adding 3, 4-ethylenedioxythiophene and the cerium-titanium-oxygen cluster prepared in the step (1) into a container filled with acetonitrile and dichloromethane in advance to obtain an initial solution, sealing the container, injecting a mixed solution of acetonitrile dissolved with iron p-toluenesulfonate and dichloromethane into the container under magnetic stirring, and stirring for 6-10 hours to react to obtain a polymerization solution;
(3)Ce@TiO2preparation of PEDOT films: will (2)Pouring the obtained polymerization solution into a spray gun, taking clean ITO glass, and spraying the clean ITO glass on a conductive surface of the ITO glass to obtain the cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film.
2. The composite film of claim 1, wherein: the mass ratio of the 3, 4-ethylenedioxythiophene to the cerium-titanium-oxygen cluster in the step (2) is 1-2: 1.
3. The composite film of claim 1, wherein: in the step (2), the volume ratio of acetonitrile to dichloromethane in the container filled with acetonitrile and dichloromethane in advance is 1-2: 1.
4. The composite film of claim 1, wherein: the total volume of the pre-filled acetonitrile and dichloromethane is 80-120 mL/g based on the mass of the 3, 4-ethylene dioxythiophene.
5. The composite film of claim 1, wherein: in the step (2), the mixed solution of acetonitrile and dichloromethane in which the iron p-toluenesulfonate is dissolved is used as a solute, the concentration of the solute is 0.01-0.02 g/mL, acetonitrile and dichloromethane are used as solvents, and the volume ratio of the acetonitrile to the dichloromethane is 1-2: 1.
6. The composite film of claim 1, wherein: the volume ratio of the mixed solution to the initial solution in the step (2) is 1-2: 1.
7. The composite film of claim 1, wherein: the speed of injecting the mixed solution into the container is 1-5 mL/min.
8. The composite film of claim 1, wherein: the mass ratio of the 3, 4-ethylenedioxythiophene to the cerium-titanium-oxygen cluster in the step (2) is 1: 1.
9. Use of the composite film according to claim 1 as an electrochromic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710767660.6A CN107602890B (en) | 2017-08-31 | 2017-08-31 | Preparation method of cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710767660.6A CN107602890B (en) | 2017-08-31 | 2017-08-31 | Preparation method of cerium-titanium-oxygen cluster/poly 3, 4-ethylenedioxythiophene composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN107602890B true CN107602890B (en) | 2021-02-02 |
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| CN101210090A (en) * | 2007-12-24 | 2008-07-02 | 重庆弈派因化工产品有限公司 | Method for preparing polyaniline/polystyrene sulfonic acid-polyvinyl alcohol electrochromism film |
| CN102604334A (en) * | 2012-02-07 | 2012-07-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film |
| CN103668529A (en) * | 2012-09-06 | 2014-03-26 | 北京服装学院 | Method of preparing compound conductive fibers, compound conductive fibers obtained by method and application of compound conductive fibers |
| CN106048710A (en) * | 2016-05-20 | 2016-10-26 | 浙江工业大学 | Erbium-doped titanium-oxygen cluster compound and preparation method and application thereof |
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| TWI273131B (en) * | 2005-12-29 | 2007-02-11 | Ind Tech Res Inst | Electrochromic film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101210090A (en) * | 2007-12-24 | 2008-07-02 | 重庆弈派因化工产品有限公司 | Method for preparing polyaniline/polystyrene sulfonic acid-polyvinyl alcohol electrochromism film |
| CN102604334A (en) * | 2012-02-07 | 2012-07-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-supporting transparent highly-conductive poly-3,4-ethylenedioxythiophene (PEDOT) film and preparation method of the film |
| CN103668529A (en) * | 2012-09-06 | 2014-03-26 | 北京服装学院 | Method of preparing compound conductive fibers, compound conductive fibers obtained by method and application of compound conductive fibers |
| CN106048710A (en) * | 2016-05-20 | 2016-10-26 | 浙江工业大学 | Erbium-doped titanium-oxygen cluster compound and preparation method and application thereof |
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