CN103146226A - Ruthenium complex dye crude product purification method with column chromatography - Google Patents
Ruthenium complex dye crude product purification method with column chromatography Download PDFInfo
- Publication number
- CN103146226A CN103146226A CN2012105806602A CN201210580660A CN103146226A CN 103146226 A CN103146226 A CN 103146226A CN 2012105806602 A CN2012105806602 A CN 2012105806602A CN 201210580660 A CN201210580660 A CN 201210580660A CN 103146226 A CN103146226 A CN 103146226A
- Authority
- CN
- China
- Prior art keywords
- alkali
- ruthenium complex
- organic solvent
- elutriant
- complex dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Hybrid Cells (AREA)
Abstract
The invention discloses a ruthenium complex dye crude product purification method with column chromatography. The method includes the following steps: step A. enabling ruthenium complex dye crude products and alkali to be heated and reacted in organic solvent to become soluble salt, and filtering; step B. filling a reverse chromatograph filled column; step C. eluting with eluant and collecting samples; step D. steaming the samples in a rotary mode to remove organic solvent, adding diluted acid for acidification, and crystallizing; and step E. cooling to achieve full crystallization, unfreezing, filtering, drying and obtaining ruthenium complex dye products. According to the method, the reverse chromatograph filled column is used for column chromatographic purification of ruthenium complex dye crude products, high-purity ruthenium complex dye products, for example, 95% ruthenium complex dye products, can be obtained with low cost.
Description
Technical field
The present invention relates to a kind of purification process of ruthenium complex dyestuff crude product.
Background technology
Current, the challenge of human maximum is exactly to seek the reproducible energy to substitute traditional petroleum-based energy, thereby satisfies the growing energy demand of the mankind.This just requires us need to seek a kind of low cost, the energy of abundant raw materials.The sun also cleans and the cheap energy with regard to therefore becoming.Photovoltaic cell also just becomes wishes the place.
Traditional photovoltaic cell, such as without machine battery CdTe etc., toxicity is higher, and natural abundance is little, and by contrast, organic battery can be avoided these problems.Dye sensitization solar battery is based on the dye cell on the nano-metal-oxide semiconductor film, and it is the battery that has color and decorate attribute.After the people such as Gratzel in 1991 have reported the great discovery of dye sensitization solar battery aspect, obtained major progress in subsequently 20 years.
Light-sensitive coloring agent is undoubtedly the important component part of battery, and it is determining the spectral absorption attribute of battery, and it has great impact for short-circuit current and open circuit voltage.In the dyestuff that battery can be used, the ruthenium complex dyestuff especially receives publicity, and it has absorption preferably at visible region, excites state lifetime long, thereby possesses feasibility.2006, it was 11% battery that sharp company announces to use N3 to make photoelectric efficiency.Gratzel group declares that also using the cell photoelectric efficient that N719 makes is 11%.Thereby the ruthenium complex dyestuff that contains dipyridyl acid has better application prospect.
Ruthenium complex dye structure formula is suc as formula shown in (I),
Wherein, R
1, R
2Be the group after heterocyclic radical, alkyl or heterocyclic radical and alkyl combination; R
3, R
4Be carboxyl or phosphate.
Also there are some problems to be solved in the ruthenium complex dyestuff, and is not high such as make photoelectric efficiency due to purification difficult.Generally document (Sauvage, F., Fischer, M.K.R., Mishra, A., Zakeeru ddin, S.M., Nazeeruddin, M.K.,
P. ， ﹠amp;
M. (2009) .A dendriticoligothiophene ruthenium sensitizer for stable dye-sensitized solar cells.Chem SusChem, 2 (8), 761-8.doi:10.1002/cssc.200900058) middle ruthenium complex dyestuff is all by purifying with expensive Sephadex-LH20 pillar.and at some document (Cao, Y., Bai, Y., Yu, Q., Cheng, Y., Liu, S., Shi, D., Gao, F., et al. (2009) .Dye-Sensitiz ed Solar Cells with a High Absorptivity Ruthenium Sensitizer Featuring a 2-(Hexylthio) thiophene Conjugated Bipyridine.The Journal of Physical Chemistry C, 113 (15), 6290-6297.doi:10.1021/jp9006872) in the record the ruthenium complex dyestuff even need to purify 3～4 times, just can reach higher degree.So purification operations has great importance for the large-scale production and application of battery.
Summary of the invention
The present invention is directed to the problem that cost for purification is high or purification process is complicated of ruthenium complex dyestuff in prior art, purpose is to provide a kind of method of utilizing column chromatography purification ruthenium complex dyestuff crude product.
The method of column chromatography purification ruthenium complex dyestuff crude product of utilizing of the present invention comprises the steps:
Steps A) ruthenium complex dyestuff crude product is become soluble salt with alkali reacting by heating in organic solvent, filter;
Step B) upper reverse chromatograms filled column;
Step C) with the elutriant wash-out and collect sample; Wherein, described elutriant comprises organic solvent, alkali and water; The volume ratio of organic solvent and water is 1～5: 1, and the volumetric molar concentration of alkali in elutriant is 0.001～0.01mol/L;
Step D) revolve the steaming sample and remove organic solvent, add the diluted acid acidizing crystal;
Step e) freezing its sufficient crystallising that makes thaws, and filters, and drying obtains the ruthenium complex dye product.
Chromatography column of the present invention has been adjusted the proportioning of elutriant simultaneously owing to having used the reverse chromatograms filler, thereby has realized higher separation efficiency.
Wherein, steps A) in, the mol ratio of ruthenium complex dyestuff crude product and alkali is preferably 1: 1～and 5, the mol ratio of alkali and organic solvent is preferably and is not less than 1: 0.5.
Wherein, step B) in, described reverse chromatograms filled column is preferably C8, the silica filler of C18 or phenyl, amino or cyano group bonding.
Step C) in, in described elutriant, the ratio of organic solvent and water is preferably 3～5: 1, and the volumetric molar concentration of alkali in elutriant is preferably 0.0015～0.0024mol/L.
Step C) in, described elutriant also comprises water; Wherein, organic solvent can be methyl alcohol, ethanol or acetonitrile; Alkali can be organic bases, and such as triethylamine, TBAH, Tetramethylammonium hydroxide etc. comprises the alkali of non-metal cations, or comprises the alkali of organic anion and metallic cation, for example sodium ethylate, potassium tert.-butoxide; Can be also mineral alkali, comprise that sodium hydroxide, potassium hydroxide etc. comprise the alkali of metallic cation and inorganic anion.
Step C) in, with pump, elutriant is pressed in post, the flow velocity of pump is 15～25mL/min.
Step B) in, anti-loaded pillar diameter to chromatograph packing material is at 8～18cm, and height is in the scope of 30～150cm.
Steps A) in, described alkali can be organic bases, and such as triethylamine, TBAH, Tetramethylammonium hydroxide etc. comprises the alkali of non-metal cations, or comprises the alkali of organic anion and metallic cation, for example sodium ethylate, potassium tert.-butoxide; Can be also mineral alkali, comprise that sodium hydroxide, potassium hydroxide etc. comprise the alkali of metallic cation and inorganic anion.Described organic solvent is methyl alcohol, ethanol or acetonitrile; Described being heated to be at 30～60 ℃ of heating 0.5～72h.Filter the filter paper use and can be at a slow speed, middling speed or filter paper fast.
Step D) in, revolve the steaming sample in 20～60 ℃ and remove organic solvent; Adding diluted acid, to be acidified to pH be crystallization between 4～7; Described diluted acid is rare nitric acid or dilute hydrochloric acid; The concentration of diluted acid used is counted 0.001～1M with monoprotic acid.
Step C) after wash-out, also further comprise with scavenging solution and clean pillar; Cleaning process in two steps, the scavenging solution of the first step is the mixed solution of tetrahydrofuran (THF), DMF, tetrahydrofuran (THF) and alkali or the mixed solution of DMF and alkali; Described alkali is triethylamine, TBAH, Tetramethylammonium hydroxide, sodium ethylate, potassium tert.-butoxide, sodium hydroxide or potassium hydroxide; Second step cleans pillar with organic solvent, and described organic solvent can be methyl alcohol, ethanol or acetonitrile.Clean complete available organic solvent and soak the reverse chromatograms filler, described organic solvent can be methyl alcohol, ethanol or acetonitrile.
Wherein, steps A) alkali and step C used in), the contained alkali of elutriant can be identical, can be also different; Steps A) organic solvent organic solvent and step C used in) in elutriant can be identical, can be also different.
Beneficial effect of the present invention is: the present invention utilizes the method for column chromatography purification ruthenium complex dyestuff crude product only to need once the ruthenium complex dyestuff to be purified at least 89.4%, even up to 95% purity.
Description of drawings
Fig. 1 is the structural representation of dye sensitization solar battery;
Fig. 2 is that purity that embodiment 1 obtains is the short-circuit current of 89.4% product, the open circuit voltage graphic representation;
Fig. 3 is that purity that embodiment 2 obtains is the short-circuit current of 90.5% product, the open circuit voltage graphic representation;
Fig. 4 is that purity that embodiment 3 obtains is the short-circuit current of 92.9% product, the open circuit voltage graphic representation;
Fig. 5 is that purity that embodiment 4 obtains is the short-circuit current of 94.5% product, the open circuit voltage graphic representation; And
Fig. 6 is that purity that embodiment 5 obtains is the short-circuit current of 95.2% product, the open circuit voltage graphic representation.
Embodiment
The dyestuff crude product that uses in the following example is CYC-B1, and it is according to document (Chen, C.-Y., Wu, S.-J., Wu, C.-G., Chen, J.-G. ， ﹠amp; Ho, K.-C. (2006) .A ruthenium complexwith superhigh light-harvesting capacity for dye-sensitized solar cells.Angewandte Chemie (International ed.in English), step in 45 (35), 5822～5.doi:10.1002/anie.200601463) is synthesized.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With column chromatography after the reverse post of C18 (diameter 9cm, height 50cm) loading, use acetonitrile: water: the elutriant wash-out of 10% TBAH=3L: 1L: 17mL (this moment, the volumetric molar concentration of alkali was about 0.0016mol/L), the flow velocity of pump is 21mL/min.Collect the sample of 30～27cm and 3～1cm during wash-out, wash-out is complete is taken up in order of priority the cleaning pillar afterwards with tetrahydrofuran (THF) 400mL and acetonitrile 2L.Solution after wash-out is regulated pH to 4.3 after overwinding steams.Freezing, filter, obtain purity after drying and be 89.4% product, Fig. 2 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of C18 (diameter 9cm, height 50cm), column chromatography after loading, use acetonitrile: water: 10% Tetramethylammonium hydroxide=3L: 1L: 20mL (volumetric molar concentration that is alkali is about 0.0019mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.Collect the sample of 30～24cm and 6～1cm during wash-out.Revolve and steam between the rear pH to 5.3 of adjusting.Freezing, filter, obtain purity after drying and be 90.5% product, Fig. 3 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of C18 (diameter 9cm, height 50cm), column chromatography after loading, elutriant are acetonitrile: water=5L: 1L, add triethylamine, and its volumetric molar concentration is 0.0015mol/L, and elutriant wash-out, the flow velocity of pump are 21mL/min.Collect the sample of 30-21cm and 9-1cm during wash-out.Revolve and steam between the rear pH to 4.5 of adjusting.Freezing, filter, obtain purity after drying and be 92.9% product, Fig. 4 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With reverse post (the diameter 9cm of C 18, height 50cm), column chromatography after loading, use methyl alcohol: water: the elutriant wash-out of 10% TBAH=3L: 1L: 23mL (volumetric molar concentration that is alkali is about 0.0022mol/L), the flow velocity of pump is 21mL/min.Collect the sample of 30～18cm and 12～1cm during wash-out.Revolve and steam between the rear pH to 4.9 of adjusting.Freezing, filter, obtain purity after drying and be 94.5% product, Fig. 5 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of C18 (diameter 9cm, height 50cm), column chromatography after loading, use acetonitrile: water: the elutriant wash-out of 10% TBAH=3L: 1L: 25mL (volumetric molar concentration that is alkali is about 0.0024mol/L), the flow velocity of pump is 21mL/min.Collect the sample of 30～17cm and 12～1cm.Revolve and steam between the rear pH to 5.1 of adjusting.Freezing, filter, obtain purity after drying and be 95.2% product, Fig. 6 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of C8 (diameter 9cm, height 50cm), column chromatography after loading, use acetonitrile: water: the elutriant wash-out of 10% TBAH=5L: 1L: 25mL (volumetric molar concentration that is alkali is about 0.0024mol/L), the flow velocity of pump is 21mL/min.Collect the sample of 30～17cm and 11～1cm during wash-out.Revolve and steam between the rear pH to 4.7 of adjusting.Freezing, filter, obtain purity after drying and be 96.4% product, Fig. 7 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of phenyl (diameter 9cm, height 50cm), column chromatography after loading, use methyl alcohol: water: the elutriant wash-out of 10% TBAH=5L: 1L: 21mL (volumetric molar concentration that is alkali is about 0.0020mol/L), the flow velocity of pump is 21mL/min.Collect the sample of 30～17cm and 10～1cm during wash-out.Revolve and steam between the rear pH to 5.4 of adjusting.Freezing, filter, obtain purity after drying and be 97.2% product, Fig. 8 is seen in the battery characterization test of products obtained therefrom.
8g ruthenium complex dyestuff dissolves in the 36mL TBAH aqueous solution and 144mL acetonitrile, is heated to 40 ℃, stirs 0.5h, filters.With the reverse post of phenyl (diameter 9cm, height 50cm), column chromatography after loading, use methyl alcohol: water: 10% TBAH=5L:1L:21mL(is that the volumetric molar concentration of alkali is about 0.0020mol/L) the elutriant wash-out, the flow velocity of pump is 21mL/min.Collect the sample of 30～17cm and 10～1cm during wash-out.Revolve and steam between the rear pH to 5.4 of adjusting.Freezing, filter, obtain purity after drying and be 97.2% product, Fig. 8 is seen in the battery characterization test of products obtained therefrom.
Effect embodiment
The ruthenium complex dyestuff that embodiment 1～8 obtains is made respectively battery, the structure of battery as shown in Figure 1, the prepared ruthenium complex dye sensitization solar battery of the present invention is by transparent substrates layer 1, conductive layer 5, light absorbing zone 4, dielectric substrate 3, consist of electrode 2,2 transparent substrates layers connect in turn is conductive layer 5, light absorbing zone 4, dielectric substrate 3 and to electrode 2, and light absorbing zone is made of semiconductor nano-particles layers 7 and dye coating 6.Wherein, semiconductor nano-particles layers 7 is connected connection with conductive layer, and dye coating 6 is connected connection with dielectric substrate
Wherein, the transparent substrates layer is glass coating, and conductive layer is FTO, and nanoparticle layers is TiO
2, dye coating namely is respectively the ruthenium complex dyestuff of embodiment 1～8 gained, and dielectric substrate is iodide ion ionogen or ionic liquid.
The performance of testing each battery according to the method for those of ordinary skills notice.Result is as shown in Fig. 2～6 and table 1.
The ruthenium complex dye product of table 1 embodiment 1～8 gained is made the performance characterization after battery
Conclusion: the purity of the ruthenium complex dye product of purifying by column chromatography method of the present invention reaches more than 89.4%, reaches as high as 97.2%.The photoelectric transformation efficiency of battery reaches as high as 7.82% more than 7.24%.
Claims (9)
1. method of utilizing column chromatography purification ruthenium complex dyestuff crude product, it comprises the steps:
Steps A) ruthenium complex dyestuff crude product is become soluble salt with alkali reacting by heating in organic solvent, filter;
Step B) upper reverse chromatograms filled column;
Step C) with the elutriant wash-out and collect sample; Wherein, described elutriant comprises organic solvent, alkali and water; The volume ratio of organic solvent and water is 1 ~ 5:1, and the volumetric molar concentration of alkali in elutriant is 0.001 ~ 0.01mol/L;
Step D) revolve the steaming sample and remove organic solvent, add the diluted acid acidizing crystal;
Step e) freezing its sufficient crystallising that makes thaws, and filters, and drying obtains the ruthenium complex dye product.
2. the method for claim 1, it is characterized in that: steps A), the mol ratio of ruthenium complex dyestuff crude product and alkali is 1: 1～5, and the mol ratio of alkali and organic solvent is not less than 1: 0.5.
3. the method for claim 1, it is characterized in that: step C), in described elutriant, the ratio of organic solvent and water is 3～5: 1, and the volumetric molar concentration of alkali in elutriant is 0.0015～0.0024mol/L.
4. the method for claim 1, it is characterized in that: step C), with pump, elutriant is pressed in post, the flow velocity of pump is 15～25mL/min.
5. the method for claim 1, it is characterized in that: step B), described reverse chromatograms filled column is C8, the silica filler of C18 or phenyl, amino or cyano group bonding.
6. the method for claim 1 is characterized in that: step B), anti-loaded pillar diameter to chromatograph packing material is at 8～18cm, and height is in the scope of 30～150cm.
7. the method for claim 1 is characterized in that: steps A) and step C) in, described organic solvent is methyl alcohol, ethanol or acetonitrile; Described alkali is organic bases or mineral alkali; Described organic bases is triethylamine, TBAH, Tetramethylammonium hydroxide, sodium ethylate or potassium tert.-butoxide; Described mineral alkali is sodium hydroxide or potassium hydroxide; Steps A) be heated to be described at 30～60 ℃ of heating 0.5～72h.
8. the method for claim 1, is characterized in that: step D), revolve the steaming sample in 20～60 ℃ and remove organic solvent; Adding diluted acid, to be acidified to pH be crystallization between 4～7; Described diluted acid is rare nitric acid or dilute hydrochloric acid; The concentration of diluted acid used is counted 0.001～1M with monoprotic acid.
9. the method for claim 1, is characterized in that: step C) after wash-out, also further comprise with scavenging solution and clean pillar; Cleaning process in two steps, the scavenging solution of the first step is the mixed solution of tetrahydrofuran (THF), DMF, tetrahydrofuran (THF) and alkali or the mixed solution of DMF and alkali; Described alkali is triethylamine, TBAH, Tetramethylammonium hydroxide, sodium ethylate, potassium tert.-butoxide, sodium hydroxide or potassium hydroxide; Second step cleans pillar with organic solvent, and described organic solvent is methyl alcohol, ethanol or acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580660.2A CN103146226B (en) | 2012-12-27 | 2012-12-27 | Ruthenium complex dye crude product purification method with column chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210580660.2A CN103146226B (en) | 2012-12-27 | 2012-12-27 | Ruthenium complex dye crude product purification method with column chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103146226A true CN103146226A (en) | 2013-06-12 |
| CN103146226B CN103146226B (en) | 2014-09-10 |
Family
ID=48544566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210580660.2A Expired - Fee Related CN103146226B (en) | 2012-12-27 | 2012-12-27 | Ruthenium complex dye crude product purification method with column chromatography |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103146226B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740127A (en) * | 2013-12-30 | 2014-04-23 | 中国科学院上海硅酸盐研究所 | Method for adsorbing and purifying ruthenium complex by using reversed phase packing |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002092569A1 (en) * | 2001-05-16 | 2002-11-21 | Sustainable Technologies International Pty Ltd | Method for large-scale manufacture of dye for dye-sensitised solar cells |
| CN1659237A (en) * | 2002-06-12 | 2005-08-24 | 巴斯福股份公司 | Method for converting perylen-3,4:9,10-tetracarboxylic acid diimides into a form suitable for use as a fluorescent dye |
| JP2009062496A (en) * | 2007-09-10 | 2009-03-26 | Sumitomo Chemical Co Ltd | Method for producing polyazo compound complex salt |
| CN101440222A (en) * | 2009-02-06 | 2009-05-27 | 中国科学院长春应用化学研究所 | Bipyridine ruthenium dye containing selenophen and use thereof in dye sensitization solar cell |
| CN101712811A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Purifying method of laser dye cumarin-4 |
| CN101855739A (en) * | 2007-11-14 | 2010-10-06 | 索尼株式会社 | Preparation of high-quality sensitizer dye for dye-sensitized solar cells |
| JP2012146632A (en) * | 2010-12-21 | 2012-08-02 | Sony Corp | Dye, dye-sensitized photoelectric conversion element, electronic device, and building |
-
2012
- 2012-12-27 CN CN201210580660.2A patent/CN103146226B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002092569A1 (en) * | 2001-05-16 | 2002-11-21 | Sustainable Technologies International Pty Ltd | Method for large-scale manufacture of dye for dye-sensitised solar cells |
| CN1659237A (en) * | 2002-06-12 | 2005-08-24 | 巴斯福股份公司 | Method for converting perylen-3,4:9,10-tetracarboxylic acid diimides into a form suitable for use as a fluorescent dye |
| JP2009062496A (en) * | 2007-09-10 | 2009-03-26 | Sumitomo Chemical Co Ltd | Method for producing polyazo compound complex salt |
| CN101855739A (en) * | 2007-11-14 | 2010-10-06 | 索尼株式会社 | Preparation of high-quality sensitizer dye for dye-sensitized solar cells |
| CN101712811A (en) * | 2008-10-06 | 2010-05-26 | 天津市化学试剂研究所 | Purifying method of laser dye cumarin-4 |
| CN101440222A (en) * | 2009-02-06 | 2009-05-27 | 中国科学院长春应用化学研究所 | Bipyridine ruthenium dye containing selenophen and use thereof in dye sensitization solar cell |
| JP2012146632A (en) * | 2010-12-21 | 2012-08-02 | Sony Corp | Dye, dye-sensitized photoelectric conversion element, electronic device, and building |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740127A (en) * | 2013-12-30 | 2014-04-23 | 中国科学院上海硅酸盐研究所 | Method for adsorbing and purifying ruthenium complex by using reversed phase packing |
| CN103740127B (en) * | 2013-12-30 | 2015-10-21 | 中国科学院上海硅酸盐研究所 | A kind of method of reverse phase filler adsorption and purification ruthenium complex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103146226B (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Srinivas et al. | D-π-A organic dyes with carbazole as donor for dye-sensitized solar cells | |
| CN110183437B (en) | Double D-pi-A type column [5] arene dye and synthetic method and application thereof | |
| JP5893390B2 (en) | Photoelectric conversion element and dye-sensitized solar cell | |
| CN103395842B (en) | Tungsten trioxide nanometer array electrochromic film and preparation method thereof | |
| WO2010104117A1 (en) | Dye-sensitized solar cell, photoelectric conversion element, and dye for use in the solar cell and the element | |
| El-Shishtawy et al. | Influence of redox electrolyte on the device performance of phenothiazine based dye sensitized solar cells | |
| CN105377996A (en) | Methine dyes with large organic counter anion for dye sensitized solar cells | |
| CN102592832B (en) | Solid electrolyte for solar cell based on ionic crystal | |
| Stathatos et al. | Dye-sensitized photoelectrochemical solar cells based on nanocomposite organic–inorganic materials | |
| Iqbal et al. | Impact of hydroxy and octyloxy substituents of phenothiazine based dyes on the photovoltaic performance | |
| CN106536531A (en) | Organic-inorganic hybrid perovskite compound, method for preparing same, and solar cell comprising same | |
| CN103588808A (en) | Polyhedral oligomeric silsesquioxane (POSS)-based solid ionic liquid, and preparation method and application thereof | |
| EP2125963A1 (en) | Noble ruthenium-type sensitizer and method of preparing the same | |
| CN104610775B (en) | A kind of phenanthro- carbazoles dyestuff and preparation method thereof and dye-sensitized solar cells | |
| CN105753769B (en) | The small molecule hole transport material and its application in perovskite battery of carbazolyl-containing and low 4- tert .-butylpyridines dosage | |
| CN105255209B (en) | Thiazolidinethione and triphenylamine light-sensitive dye and preparation method thereof | |
| CH699662B1 (en) | Solar cell with ruthenium complex. | |
| CN102618066A (en) | Organic dye containing calixarene derivative and preparation method and application thereof | |
| CN103146226B (en) | Ruthenium complex dye crude product purification method with column chromatography | |
| CN103145761A (en) | Ruthenium complex crude product purification method with recrystallization | |
| CN101165103A (en) | Indoline-like photosensitive dyestuff and application thereof | |
| CN105647226A (en) | Organic photosensitive dye, preparation method therefor and application thereof in solar cells | |
| CN105219119B (en) | A kind of thiazolone anthracene amine light-sensitive coloring agent and preparation method thereof | |
| CN108219512A (en) | Indoline-quinoxaline-dithieno quinoxaline dyestuff and its application in dye-sensitized solar cells | |
| CN104403351A (en) | Organic photosensitive dye based on symmetrical diketopyrrolopyrrole as conjugate bridge |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140910 Termination date: 20171227 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |