CN110183437B - Double D-pi-A type column [5] arene dye and synthetic method and application thereof - Google Patents
Double D-pi-A type column [5] arene dye and synthetic method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a double D-pi-A type column [5] arene dye and a synthesis method and application thereof. The double D-pi-A type column [5] arene dye has a conjugated structure, and the synthesis and the application thereof in dye-sensitized solar cells. The invention takes the benzene ring of the alkoxy column [5] arene as a conjugated bridging structure, increases the conjugation of dye molecules, strengthens the molar absorption coefficient of the dye and widens the light-capturing range of the dye by bridging two left and right D-Pi-A structural units through the alkoxy column [5] arene, and inhibits the aggregation of the dye molecules by using the three-dimensional space structure of the column arene. The dye has excellent light-capturing capability, and the dye-sensitized solar cell constructed by the dye can obtain larger photocurrent and voltage, so that higher photoelectric conversion efficiency is obtained.
Description
Technical Field
The invention relates to the field of photoelectric conversion material application in fine chemical engineering and the technical field of dye-sensitized solar cells, in particular to a double D-pi-A type column [5] arene dye, a synthetic method and application thereof.
Background
Dye-sensitized solar cells (DSSCs) are a new class of flexible devices that convert solar energy into electrical energy. The battery has high energy conversion efficiency under outdoor light and indoor weak light because of simple and convenient preparation, so that the battery can be applied to the commercial fields of indoor decoration, building curtain walls and the like, and attracts the attention of the market. The method has the advantages of small amount of dye, low cost, simple and repeatable preparation process, and can prepare a large number of devices through dye bath. For a high performance dye-sensitized solar cell, the structure of the sensitizing dye is crucial and plays a crucial role in the photoelectric conversion efficiency of the cell. At present, dyes with the highest photoelectric conversion efficiency based on iodine-based electrolyte are polypyridine ruthenium and metalloporphyrin complex dyes, the two high-efficiency dyes are metal complexes, the preparation process is long, and separation and purification are relatively difficult. The pure organic dye has the advantages of simple synthesis, easy design and modification of molecular structure, high molar extinction coefficient and the like, and is widely developed and applied.
The D-pi-A structure can effectively capture solar photons through intramolecular photoelectron transfer, and is proved to be a structure required by efficient dye molecules. The double (D-pi-A) type dye has two independent D-pi-A structural units in one dye molecule, so that the double-rate light-capturing unit is equivalent to one molecule, and the light-capturing capacity is obviously enhanced. Meanwhile, the column [5] arene has an excellent spatial three-dimensional structure, can effectively support pi-pi accumulation of dye molecules caused by a conjugated surface, and inhibits pi-pi aggregation among molecules through a conjugated bridging structure provided by a benzene ring. At present, no bilateral dye taking column [5] arene as a conjugated bridging structure is reported.
The invention designs and synthesizes a pure organic dye which takes column [5] arene as a conjugated bridging structure and has a double (D-pi-A) structure. The dye has the advantages of simple structure, easy synthesis, good photoelectric conversion performance and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a synthetic method and application of a double D-pi-A type column [5] arene dye.
The invention aims to provide a double D-pi-A type column [5] arene dye for inhibiting aggregation and enhancing light capturing capacity aiming at the serious aggregation of the existing dye for DSSCs. The dye is a bilateral pure organic dye which takes alkoxy column [5] arene as a bridging structure, phenothiazine as an electron donor, thiophene/furan as a pi bridge and cyanoacetic acid as an electron acceptor and an anchoring group. The dye has good application performance on the dye-sensitized solar cell.
The double D-Pi-A type column [5] arene dye provided by the invention has the advantages of simple preparation method and process, high efficiency, capability of effectively carrying out large-scale production and universality.
The invention also provides application of the double D-pi-A type column [5] arene dye in DSSCs, particularly application of the double D-pi-A type column arene dye as a sensitizer to a photoanode of a DSSCs device, which can effectively inhibit electron recombination and improve open-circuit voltage, and the double D-pi-A structure enhances the light-capturing capability of the dye and effectively improves short-circuit current, thereby effectively improving the photoelectric performance of dye-sensitized solar cells.
According to the synthesis method provided by the invention, two units with D-pi-A structures are introduced into two sides of column [5] arene with a spatial three-dimensional structure through a conjugated structure, so that the double D-pi-A type column [5] arene dye is obtained, and the dye can be applied to preparation of dye-sensitized solar cells.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a double D-pi-A type column [5] arene dye, which has the following structural general formula:
wherein the value of n is 0-3; r1Is branched chain with 1-20 carbon atoms or straight-chain alkyl with 1-20 carbon atoms; r2Is straight-chain alkyl with 1-4 carbon atoms; x is an O atom or an S atom.
The invention provides a method for synthesizing the double D-pi-A type column [5]]The method of the aromatic hydrocarbon dye is that when the value of n is 0 to 3, R1Is branched alkyl with 1-20 carbon atoms or straight-chain alkyl with 1-20 carbon atoms, R2Is straight-chain alkyl with 1-4 carbon atoms and X is O atom or S atom, and comprises the following steps:
the intermediate 1 is subjected to bromination reaction with N-bromosuccinimide at room temperature, and the intermediate 2 is efficiently prepared; the intermediate 2 is converted into a pinacol ester structure of phenylboronic acid of the intermediate 3 under the catalysis of divalent palladium; further synthesizing the intermediate 3 and the intermediate 4 into a key intermediate 5 efficiently under the catalysis of zero-valent palladium and under the normal pressure condition; at room temperature, the key intermediate 5 is hydrolyzed in trifluoroacetic acid to obtain the double D-pi-A type column [5] arene dye.
The double D-pi-A type column [5] arene dye provided by the invention can be applied to the preparation of dye-sensitized solar cells.
Further, when the double D-pi-A type column [5] arene dye provided by the invention is applied to the preparation of a dye-sensitized solar cell, the method comprises the following steps:
(1) adding the double D-pi-A type column [5] arene dye into an organic solvent, and completely dissolving to obtain a dye solution;
(2) will adsorb nano TiO2Thin film transparent conductive glass (SnO with F doping)2Coating glass, FTO) is soaked in the solution of the dye in the step (1) for dye bath treatment to obtain a photo-anode;
(3) depositing a Pt catalyst layer in the middle of another piece of transparent conductive glass to be used as a photocathode; nano TiO attached with the photo-anode2And arranging the thin film layer and the photocathode catalyst layer in a face-to-face manner, sealing the periphery of the thin film layer and the photocathode catalyst layer into a closed cavity, and filling electrolyte into the cavity to obtain the dye-sensitized solar cell.
Further, the organic solvent in the step (1) is a mixed solvent of chloroform and ethanol, wherein the volume ratio of chloroform to ethanol is 1-5: 1.
further, the concentration of the solution of the dye in the step (1) is 1-5X 10-4M。
Preferably, the transparent conductive glass in the step (2) is SnO with doped F2Coated glass; the nano TiO2The thickness of the film is 5-17 mu m, and the nano TiO2The length of the film is 4mm, and the nano TiO2The width of the film was 3 mm.
Preferably, with a transparent conductive layer (F-doped SnO)2Coating) has a glass width of 1.2cm and a length of 1.7 cm;
further, the dye bath treatment in the step (2) is carried out in a dark environment, and the time of the dye bath treatment is 6-24 hours.
Further, the electrolyte solution in the step (3) contains 1, 2-dimethyl-3-propyl imidazolium iodide with the concentration of 0.3-0.6M, LiI with the concentration of 0.1M and I with the concentration of 0.05M2And a 0.5M solution of 4-tert-butylpyridine in acetonitrile.
The synthesis method of the bis (D-Pi-A) dye containing the column [5] arene is simple, the raw materials are cheap and easy to obtain, and the synthesis is carried out according to the following reaction formula by way of example:
synthesis from intermediate 1 to intermediate 2:
dissolving 1 part of intermediate 1 in redistilled tetrahydrofuran as a solvent, cooling to 0 ℃ in an ice water bath, and dropwise adding 1.2 parts of NBS tetrahydrofuran solution to naturally react for 12 hours at normal temperature; pouring into water, adding dichloromethane for extraction, washing an organic layer with water, drying, concentrating, and separating and purifying a crude product by column chromatography, wherein the eluent ratio is petroleum ether: dichloromethane: ethyl acetate 30:1:1 (v/v).
Synthesis from intermediate 2 to intermediate 3:
weighing 1 part of intermediate 2, 2 parts of pinacol ester diborate, 2 parts of potassium acetate and steamed 1, 4-dioxane in a two-mouth reaction bottle, and pumping and replacing argon for 3 times; under an inert atmosphere, adding a catalytic amount of Pd (dppf)2Cl2Stirring at room temperature for 5-10min, heating to 100 ℃, reacting overnight, monitoring by TLC, and using petroleum ether as a developing agent: dichloromethane: ethyl acetate 20:2:1 (v/v); cooling, adding water into the reaction bottle, extracting with dichloromethane, washing the organic layer with water, drying, concentrating, and separating and purifying the crude product by column chromatography.
The synthesis method of the intermediate 5 comprises the following steps:
under an Ar atmosphere, 1 part of intermediate 4 and 2.3 parts of intermediate 3, 0.1 part of Pd (PPh) were added in tetrahydrofuran/water (v/v ═ 4:1) as a solvent3)45 parts of anhydrous K2CO3(ii) a Heating to 70 ℃ and reacting for 24 h; cooling, adding water into the reaction bottle, extracting with dichloromethane, washing the organic layer with water, drying, and concentrating the crude product to purify by column chromatography, wherein the ratio of petroleum ether: dichloromethane: ethyl acetate 10:1:1(v/v) was passed through the column.
The synthesis method of the target dye comprises the following steps:
transferring the purified and dried intermediate 5 into a single-mouth reaction bottle, adding 20mL of trifluoroacetic acid, and stirring at room temperature in a dark place for reacting for 4-8 h; and pouring the reaction liquid into deionized water under stirring, filtering and collecting the solid after the solid is separated out, repeatedly washing the solid with the deionized water until the pH of the liquid generated by washing is neutral, and drying to obtain the double D-pi-A type column [5] arene dye.
The dye material sensitized solar cell prepared from the synthesized double D-Pi-A type column [5] arene dye is tested for cell performance, and the measured photoelectric conversion efficiency is 7.1-8.3%.
The performance test comprises the following steps: leading out wires from the photo-anode and the photo-cathode of the dye-sensitized solar cell respectively, connecting the wires to a cell performance testing device (Keithley 2400), and adjusting the light intensity to 100mW/cm by using a solar simulator model (Newport-94043A, 450W xenon lamp, AM1.5G filter)2The working area of the battery is 0.12cm2And the photoelectric conversion efficiency of the dye-sensitized cell is 7.1-8.3% based on the J-V curve of the dye-sensitized cell.
Compared with the prior art, the invention has the following advantages and beneficial effects:
in order to inhibit aggregation among dye molecules, the double D-Pi-A type column [5] arene dye provided by the invention synthesizes a double D-Pi-A type column [5] arene dye by introducing two D-Pi-A structures into one dye molecule; the double D-pi-A type column [5] arene dye can be applied to the preparation of a dye-sensitized solar cell, and the open-circuit voltage of the dye-sensitized solar cell can be improved; the absorption capacity of the cell to sunlight is enhanced, and the short-circuit current is improved, so that the dye-sensitized solar cell based on the dye can obtain large photovoltage and photocurrent, and higher photoelectric conversion efficiency is obtained.
Drawings
FIG. 1 is a UV/Vis absorption spectrum of the dye synthesized in example 1 in chloroform solution.
Fig. 2 is a current-voltage curve measured for a dye-assembled cell synthesized in example 1.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Synthesis of double D-pi-A type column [5] arene dye
By way of example, the structure of the bis D-. pi. -A type pillared [5] arene dye synthesized in example 1 is as follows:
n is 1, R1Is a branched alkyl group of 8 carbon atoms, R2Is alkyl with 1 carbon atom; x is an S atom.
The method for synthesizing the double D-pi-A type column [5] arene dye comprises the following steps:
(1) synthesis of Compound 2
Taking redistilled tetrahydrofuran as a solvent, dissolving 3.11g (5mmol) of the compound 1, cooling to 0 ℃ in an ice-water bath, dropwise adding a tetrahydrofuran solution dissolved with 1.068g (6mmol) of NBS, and naturally heating to normal temperature for reaction for 12 hours. Pouring into water, adding dichloromethane for extraction for 3 times, washing an organic layer with saturated salt water, combining organic phases, drying, concentrating, and separating and purifying a crude product by column chromatography, wherein the eluent ratio is petroleum ether: dichloromethane: ethyl acetate 30:1:1(v/v/v), the title product was spin-dried to give 2.86g of a dark red solid, yield: 80 percent. The melting point is 123.8-125.1 ℃.
1H NMR(400MHz,Chloroform-d，ppm)δ8.15(s,1H),8.64-8.65(d,J＝3.8Hz,1H),7.39(s,1H),7.21-7.25(m,5H),7.08-7.13(m,3H),6.12-6.13(d,J＝3.8Hz,1H),6.10-6.11(d,J＝4.2,1H),3.92-3.93(d,J＝5.5,2H),1.75-1.81(m,1H),1.56(s,9H),1.42-1.53(m,4H),1.31-1.40(m,4H),0.95(m,6H).
(2) Synthesis of Compound 3
Weighing 1.43g (2mmol) of the above compound 2, 1.01g (4mmol) of pinacol diboron, 0.39g (4mmol) of potassium acetate and 50mL of redistilled 1, 4-dioxane in a 100mL two-neck reaction flask, evacuating argon for 3 times, adding a catalytic amount of Pd (dppf)2Cl2Stirring for 5-10min at room temperature, heating the oil bath to 100 ℃, and stirring for 24 hours to finish the reaction. After cooling to room temperature, the reaction mixture was poured into water, extracted 3 times with 25mL of dichloromethane, the organic phases were combined, washed with brine and dried over anhydrous sodium sulfate, the dichloromethane was removed by rotary evaporation, and the residue was extracted with petroleum ether: dichloromethane: purification by silica gel column chromatography with ethyl acetate 20:2:1(v/v/v) as eluent, and drying in vacuo gave a brownish black solid 3(961mg,1.3mmol), 64% yield, melting point: 169.2-171.5 ℃.
1H NMR(400MHz,Chloroform-d，ppm)δ8.15(s,1H),7.64-7.65(d,J＝3.9Hz,1H),7.39(s,1H),7.20-7.25(m,5H),7.09-7.13(m,3H),6.12-6.13(d,J＝2.8Hz,1H),6.10-6.11(d,J＝3.4,1H),3.92-3.94(d,J＝5.6,2H),1.75-1.81(m,1H),1.56(s,9H),1.44-1.51(m,4H),1.30-1.36(m,4H),1.30(s,12H),0.95(m,6H).
(3) Synthesis of Compound 5
0.8876mg (0.876mmol, 1eq) of compound 4, 1.4953g (1.9597mmol, 2.3eq) of compound 3, 464mg (4.4mmol, 5eq) of anhydrous sodium carbonate are weighed, transferred to a 100mL two-necked reaction flask, 50mL of a tetrahydrofuran/water (v/v ═ 4:1) mixed solvent is added, argon is purged, and a catalytic amount of Pd (PPh) is added3)4Stirring for 10 minutes at room temperature, heating the oil bath kettle to 70 ℃, and stirring for 24 hours to finish the reaction. Cooling to room temperature, pouring the reaction solution into water, extracting with 25mL dichloromethane for 3 times, combining organic phases, washing with saturated brine, drying with anhydrous sodium sulfate,the dichloromethane was removed by rotary evaporation and the residue was purified by distillation with petroleum ether: dichloromethane: purification by silica gel column chromatography with ethyl acetate 10:1:1(v/v/v) as eluent gave 4 as a black solid (1.19g,0.56mmol) after vacuum drying in 64% yield. Melting point: 218.3-220.7 ℃.
1H NMR(400MHz,Chloroform-d，ppm)δ8.15(s,2H),7.63(d,J＝4.0Hz,2H),7.30–7.27(m,6H),7.21-7.24(m,4H),7.12-7.17(m,8H),7.98–7.00(m,4H),6.67-6.68(d,J＝2.8Hz,4H),6.63-6.64(d,J＝3.4Hz,2H),6.54(s,2H),6.19(s,2H),6.17(s,2H),6.10(s,2H),4.11-4.15(d,J＝14.0Hz,2H),3.94-3.95(d,J＝5.6Hz,4H),3.82-3.85(d,J＝14.1Hz,2H),3.82(s,2H),3.74(s,4H),3.60(s,6H),3.52(s,6H),3.41(s,6H),3.34(s,6H),1.77-1.83(m,2H),1.57(s,18H),1.44-1.54(m,8H),1.32-1.40(m,8H),0.91-1.02(m,12H).
(4) Synthesis of Compound 6
637mg (0.3mmol) of Compound 5 dried under vacuum were added directly to a 50mL single-necked flask, and trifluoroacetic acid (20mL) was added thereto and stirred at room temperature for 6 hours. After the reaction, the reaction solution was poured into 200mL of deionized water. Stirring at 600rpm for 60 minutes to precipitate solids, collecting the solids by filtration, and repeatedly washing with deionized water until the pH of the liquid produced by the washing is neutral. The solid was dried to give a black solid, pillar aromatic phenothiazine dye (537mg,0.13mmol), 89% yield, melting point 264.3-267.7 ℃.
1H NMR(400MHz,THF-d8,ppm)δ10.69(s,2H),8.20(s,2H),7.69-7.70(d,J＝3.9Hz,2H),7.33-7.34(m,4H),7.22-7.27(m,6H),7.12–7.16(m,8H),7.06(d,J＝3.5Hz,2H),6.97-6.98(d,J＝8.5Hz,2H),6.69-6.70(d,J＝3.5Hz,2H),6.65(s,4H),6.54(s,2H),6.13-6.14(d,J＝3.0Hz,2H),6.11-6.12(d,J＝2.9Hz,2H),6.00(s,2H),3.98-4.01(d,J＝13.7Hz,2H),3.89-3.90(d,J＝5.4Hz,4H),3.77-3.80(d,J＝13.6Hz,2H),3.67(s,2H),3.58(s,4H),3.53(s,6H),3.50(s,6H),3.41(s,6H),3.28(s,6H),1.66-1.72(m,2H),1.36-1.53(m,8H),1.25-1.34(m,8H),0.83-0.91(m,12H).
Example 2
The double D-pi-A type column [5] arene dye prepared in the example 1 is subjected to an ultraviolet-visible absorption spectrum test, and the ultraviolet-visible absorption spectrum is shown in a figure 1.
The relevant parameters and instruments of the ultraviolet-visible absorption spectrum test are shown as follows.
Solvent: chloroform;
concentration: 2X 10-5M；
Temperature: room temperature;
the instrument comprises the following steps: shimadzu UV-2450 ultraviolet visible spectrophotometer.
From FIG. 1, it can be seen that the double D-. pi. -A type column [5] obtained in example 1 was used in chloroform solution]The aromatic hydrocarbon dye is represented as two main absorption peaks, one is an absorption peak of pi-pi transition, the other is an absorption peak of Intramolecular Charge Transfer (ICT), the molar extinction coefficient of the dye is higher, the absorption range is wide, and the absorption range exceeds 30000M within the range of 400-550nm-1·cm-1This indicates that the dye has good light trapping ability.
Example 3
The application of the double D-pi-A type column [5] arene dye prepared in the embodiment 1 in the preparation of the dye-sensitized solar cell comprises the following steps:
(1) with transparent conductive layer (F-doped SnO)2Coating) glass pretreatment: the cut FTO (1.2 cm wide and 1.7cm long) was ultrasonically cleaned and rinsed several times with deionized water. And then soaking in a saturated ethanol solution of KOH for 24 hours. Then ultrasonic cleaning is carried out by deionized water, acetone, deionized water and ethanol in sequence, and the mixture is dried and stored for standby;
(2)TiO2preparing nanocrystalline slurry: at room temperature, 15mL of Ti (OBu)2A mixture of 20mL EtOH was stirred vigorously (600 rmp rpm) with the addition of 50mL acetic acid and deionized water and stirring was continued for 1 h. The mixture was placed in an autoclave lined with Teflon (polytetrafluoroethylene) and treated at 230 ℃ for 12 hours, followed by natural cooling to room temperature. Filtering the obtained suspension, taking precipitate, washing with deionized water and ethanol for multiple times in sequence, and drying in an oven at 50 ℃ for 6h to obtain TiO2Nanocrystalline particles. To the prepared TiO2After adding ethanol, acetic acid, terpineol and ethyl cellulose to the nanocrystalline particles, respectively, the mixture is ground to obtain a slurry-like substance. Obtaining the required white viscous TiO by ultrasonic2And (4) nano-crystal slurry.
(3) Nanocrystalline TiO2Preparation of the film: the treated conductive glass is placed with the conductive surface facing upwards, a silk screen plate is placed above the glass, the mesh distance of 1cm is controlled, and the prepared TiO is2And placing the nano-crystal slurry on a silk screen for printing. Controlling TiO2The film thickness was 12 μm (area 3X 4 mm). The prepared photo-anode needs to be put into an oven to be dried at 125 ℃. And sequentially treating at different temperatures in a muffle furnace (325 deg.C for 5min, 375 deg.C for 5min, 450 deg.C for 15min, and 500 deg.C for 15min) to remove organic substances on the film. Then dipped in the prepared 0.2M TiCl4Treating in water solution for half an hour. And (4) after the treatment is finished, washing the substrate by using deionized water and ethanol, and baking the substrate again for 30min in a muffle furnace at the temperature of 500 ℃. Cooling to 70 ℃ for later use;
(4) preparing a dye solution: the double D-pi-A type column [5] obtained in example 1 was used]Dissolving aromatic dye in chloroform solution to obtain 2 × 10 solution-4mol·L-1A dye solution;
(5) preparing an electrolyte solution: a mixture containing 1, 2-dimethyl-3-propylimidazolium iodide at a concentration of 0.6M, LiI at a concentration of 0.1M, and I at a concentration of 0.05M was prepared2And a 0.5M acetonitrile solution of 4-tert-butylpyridine;
(6) sensitization of the photo-anode: soaking the photoanode prepared in the step (3) in the dye solution prepared in the step (4) for 12 hours in a dark and light-proof environment, taking out, washing the surface with ethanol to remove the dye residual or physically adsorbed on the surface of the membrane, drying, and storing the dry and light-proof environment for packaging for later use;
(7) assembling the battery: TiO of photo-anode for completing sensitization2Coating insulating epoxy resin film and TiO around the film2The layer is in the middle. To TiO 22Dripping 1-2 drops of electrolyte on the surface of the membrane (prepared in step (5)), and covering the platinum counter electrode on the photo-anode (punching, removing air bubbles and sealing with epoxy resin) And fixing the two sides by using a clamp to form the open sensitized dye solar cell to be detected, thereby obtaining the dye sensitized solar cell.
Example 4
And (3) testing the performance of the dye-sensitized solar cell:
lead wires were led out from the photo-anode and the photo-cathode of the dye-sensitized solar cell prepared in example 3, respectively, and connected to a cell performance testing apparatus (Keithley 2400), and the light intensity was adjusted to 100mW/cm using a solar simulator model (Newport-94043A, 450W xenon lamp, am1.5g filter)2The working area of the battery is 0.12cm2The J-V curve of the dye-sensitized cell was tested.
The measured J-V curves are shown in FIG. 2, and the data are summarized in Table 1 (Table 1 is a data table showing the performance of the dye-sensitized solar cell obtained in example 3 and the performance of the solar cell obtained by the conventional dye).
TABLE 1
The solar cell performance parameters prepared from dye a, which is referred to in example 1, are from Org Electron,14(2013),2662-2672.
As can be seen from the data of fig. 2 and table 1, the solar cell prepared using the dye obtained in example 1 exhibited higher photoelectric conversion efficiency, possessed higher short-circuit current and open-circuit voltage. Mainly because the bis (D-Pi-A) column [5] arene dye has better light capture capability and high efficiency of electron injection into titanium dioxide, and the column arene inhibits electron recombination; from the data in table 1, the solar cell prepared by the dye provided by the present invention has better performance than the solar cell prepared by the existing dye a.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (9)
1. A double D-pi-A type column [5] arene dye is characterized by having a structural general formula as follows:
wherein the value of n is 0-3; r1Is branched alkyl with 1-20 carbon atoms or straight-chain alkyl with 1-20 carbon atoms; r2Is straight-chain alkyl with 1-4 carbon atoms; x is an O atom or an S atom.
2. A method for synthesizing a bis D-pi-a type column [5] arene dye according to claim 1, comprising the steps of:
the intermediate 1 is subjected to bromination reaction with N-bromosuccinimide at room temperature to prepare an intermediate 2; intermediate 2 in Pd (dppf)2Cl2Is converted into a phenylboronic acid pinacol ester structure of an intermediate 3 under the catalysis of the (A); further intermediates 3 and 4 in Pd (PPh)3)4Under the catalysis of (3), synthesizing a key intermediate 5 under the normal pressure condition; hydrolyzing the key intermediate 5 in trifluoroacetic acid to obtain the double D-pi-A type column [5]]An aromatic hydrocarbon dye.
3. The use of the bis-D-pi-a type column [5] arene dye of claim 1 in the preparation of dye-sensitized solar cells.
4. Use according to claim 3, characterized in that it comprises the following steps:
(1) adding the double D-pi-A type column [5] arene dye into an organic solvent, and uniformly mixing to obtain a dye solution;
(2) will adsorb nano TiO2Soaking transparent conductive glass of the film in the solution of the dye in the step (1)Carrying out dye bath treatment to obtain a photo-anode;
(3) depositing a Pt catalyst layer in the middle of another piece of transparent conductive glass to be used as a photocathode; nano TiO attached with the photo-anode2And arranging the thin film layer and the photocathode catalyst layer in a face-to-face manner, sealing the periphery of the thin film layer and the photocathode catalyst layer into a closed cavity, and filling electrolyte into the cavity to obtain the dye-sensitized solar cell.
5. The use according to claim 4, wherein the organic solvent in step (1) is a mixed solvent of chloroform and ethanol, wherein the volume ratio of chloroform to ethanol is 1-5: 1.
6. the use according to claim 4, wherein the dye of step (1) is in a solution having a concentration of 1-5 x 10- 4M。
7. The use according to claim 4, wherein the transparent conductive glass in the step (2) is SnO with doped F2Coated glass; the nano TiO2The thickness of the film is 5-17 μm.
8. The use according to claim 4, wherein the dye bath treatment of step (2) is carried out in a dark environment, and the time of the dye bath treatment is 6-24 hours.
9. The use according to claim 4, wherein the electrolyte solution of step (3) comprises 1, 2-dimethyl-3-propyl imidazolium iodide with a concentration of 0.3-0.6M, LiI with a concentration of 0.1M, and I with a concentration of 0.05M2And a 0.5M solution of 4-tert-butylpyridine in acetonitrile.
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| PCT/CN2019/113790 WO2020232973A1 (en) | 2019-05-21 | 2019-10-28 | DOUBLE D-π-A TYPE PILLAR[5]ARENE DYE, SYNTHESIS METHOD AND APPLICATION THEREOF |
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| CN110437822A (en) * | 2019-08-23 | 2019-11-12 | 西北民族大学 | One kind being based on the supermolecule white light emitting material and preparation method thereof of column [5] aromatic hydrocarbons |
| CN111423365B (en) * | 2020-04-03 | 2020-11-20 | 华东师范大学 | Bifunctional group pillar aromatic hydrocarbon derivative ligand, metal organic cage and preparation method |
| CN112011034B (en) * | 2020-08-19 | 2021-09-28 | 盐城海关综合技术服务中心 | Dimethoxy column [ n ] arene knotting conjugated polymer and preparation method and application thereof |
| CN113200941B (en) * | 2021-04-21 | 2022-08-26 | 华东理工大学 | Column aromatic hydrocarbon fluorescent adsorption material containing phenothiazine and preparation method thereof |
| CN113980009B (en) * | 2021-10-08 | 2023-08-22 | 华南理工大学 | AIE column aromatic fluorescent probe for diamine detection and preparation method and application thereof |
| CN114479838B (en) * | 2022-01-20 | 2023-10-31 | 常州大学 | Light capturing system based on column arene and preparation method and application thereof |
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| CN115672295B (en) * | 2022-11-05 | 2023-12-15 | 中国科学院兰州化学物理研究所 | Preparation and application of imine type column [5] arene modified silica gel chromatographic packing |
| CN115739054A (en) * | 2022-11-09 | 2023-03-07 | 兰州城市学院 | Preparation and application of carboxylic acid column [5] arene modified attapulgite |
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