CN103146226B - Ruthenium complex dye crude product purification method with column chromatography - Google Patents
Ruthenium complex dye crude product purification method with column chromatography Download PDFInfo
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- CN103146226B CN103146226B CN201210580660.2A CN201210580660A CN103146226B CN 103146226 B CN103146226 B CN 103146226B CN 201210580660 A CN201210580660 A CN 201210580660A CN 103146226 B CN103146226 B CN 103146226B
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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 find the reproducible energy to substitute traditional petroleum-based energy, thereby meets the growing energy demand of the mankind.This just requires us need to find a kind of low cost, the energy of abundant raw materials.Therefore the sun also just becomes the clean and cheap energy.Photovoltaic cell also just becomes and wishes 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 the dye cell based on nano-metal-oxide semiconductor film, and it is the battery that has color and decorate attribute.Since the people such as Gratzel in 1991 have reported after the great discovery of dye sensitization solar battery aspect, in subsequently 20 years, obtained major progress.
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 can use at battery, ruthenium complex dyestuff especially receives publicity, and it has good absorption in visible region, and the life-span of excited state is long, thereby possesses feasibility.2006, it was 11% battery that sharp company announce to be used N3 to make photoelectric efficiency.Gratzel group also declares that using the cell photoelectric efficiency that N719 makes is 11%.Thereby there is better application prospect containing the ruthenium complex dyestuff of dipyridyl acid.
Ruthenium complex dye structure formula is suc as formula shown in (I),
formula (I)
Wherein, R
1, R
2for the group after heterocyclic radical, alkyl or heterocyclic radical and alkyl combination; R
3, R
4for carboxyl or phosphate.
Also there are some problems to be solved in ruthenium complex dyestuff, 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., &
m. (2009) .A dendritic oligothiophene ruthenium sensitizer for stable dye-sensitized solar cells.Chem SusChem, 2 (8), 761 – 8.doi:10.1002/cssc.200900058) in, 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 a2-(Hexylthio) thiophene Conjugated Bipyridine.The Journal of Physical Chemistry C, 113 (15), 6290 – 6297.doi:10.1021/jp9006872) the ruthenium complex dyestuff of recording in even needs 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, object 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 to soluble salt with alkali reacting by heating in organic solvent, filter;
Step B) upper reverse chromatograms filled column;
Step C) with 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 steaming sample and remove organic solvent, add diluted acid acidizing crystal;
Step e) freezing its sufficient crystallising that makes, thaws, and filters, the dry ruthenium complex dye product that obtains.
Chromatography column of the present invention, owing to having used reverse chromatograms filler, has been adjusted the proportioning of elutriant simultaneously, thereby has realized higher separation efficiency.
Wherein, steps A) in, the mol ratio of ruthenium complex dyestuff crude product and alkali is preferably 1:1～5, and 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, the alkali that such as triethylamine, TBAH, Tetramethylammonium hydroxide etc. comprises non-metal cations, or the alkali that comprises organic anion and metallic cation, for example sodium ethylate, potassium tert.-butoxide; Also can be mineral alkali, comprise the alkali that sodium hydroxide, potassium hydroxide etc. comprise 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, the 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, the alkali that such as triethylamine, TBAH, Tetramethylammonium hydroxide etc. comprises non-metal cations, or the alkali that comprises organic anion and metallic cation, for example sodium ethylate, potassium tert.-butoxide; Also can be mineral alkali, comprise the alkali that sodium hydroxide, potassium hydroxide etc. comprise 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, in 20～60 ℃, revolve steaming sample 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; 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 to cleaning process; 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 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 need to once ruthenium complex dyestuff can be purified to at least 89.4%, even up to 95% purity.
Accompanying drawing explanation
Fig. 1 is the structural representation of dye sensitization solar battery;
Fig. 2 is the short-circuit current of purity that embodiment 1 the obtains product that is 89.4%, open circuit voltage graphic representation;
Fig. 3 is the short-circuit current of purity that embodiment 2 the obtains product that is 90.5%, open circuit voltage graphic representation;
Fig. 4 is the short-circuit current of purity that embodiment 3 the obtains product that is 92.9%, open circuit voltage graphic representation;
Fig. 5 is the short-circuit current of purity that embodiment 4 the obtains product that is 94.5%, open circuit voltage graphic representation; And
Fig. 6 is the short-circuit current of purity that embodiment 5 the obtains product that is 95.2%, open circuit voltage graphic representation.
Fig. 7 is the short-circuit current of purity that embodiment 6 the obtains product that is 96.4%, open circuit voltage graphic representation;
Fig. 8 is the short-circuit current of purity that embodiment 7 the obtains product that is 97.2%, open circuit voltage graphic representation.
Embodiment
The dyestuff crude product using in the following example is CYC-B1, it is according to document (Chen, C.-Y., Wu, S.-J., Wu, C.-G., Chen, J.-G., & Ho, K.-C. (2006) .A ruthenium complex with superhigh light-harvesting capacity for dye-sensitized solar cells.Angewandte Chemie (International ed.in English), 45 (35), 5822～5.doi:10.1002/anie.200601463) step in is synthesized.
Embodiment 1
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, with acetonitrile: water: the 10% TBAH=3L:1L:17mL(now volumetric molar concentration of alkali is about 0.0016mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～27cm and 3～1cm, after wash-out, with tetrahydrofuran (THF) 400mL and acetonitrile 2L, be taken up in order of priority cleaning pillar.Solution after wash-out regulates pH to 4.3 after overwinding steams.Freezing, filter, obtain purity after dry and be 89.4% product, Fig. 2 is shown in the battery characterization test of products obtained therefrom.
Embodiment 2
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, with acetonitrile: water: 10% Tetramethylammonium hydroxide=3L:1L:20mL(is that the volumetric molar concentration of alkali is about 0.0019mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～24cm and 6～1cm.Revolve and steam between the rear pH to 5.3 of adjusting.Freezing, filter, obtain purity after dry and be 90.5% product, Fig. 3 is shown in the battery characterization test of products obtained therefrom.
Embodiment 3
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 is acetonitrile: water=5L:1L, adds triethylamine, its volumetric molar concentration is 0.0015mol/L, elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30-21cm and 9-1cm.Revolve and steam between the rear pH to 4.5 of adjusting.Freezing, filter, obtain purity after dry and be 92.9% product, Fig. 4 is shown in the battery characterization test of products obtained therefrom.
Embodiment 4
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, with methyl alcohol: water: 10% TBAH=3L:1L:23mL(is that the volumetric molar concentration of alkali is about 0.0022mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～18cm and 12～1cm.Revolve and steam between the rear pH to 4.9 of adjusting.Freezing, filter, obtain purity after dry and be 94.5% product, Fig. 5 is shown in the battery characterization test of products obtained therefrom.
Embodiment 5
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, with acetonitrile: water: 10% TBAH=3L:1L:25mL(is that the volumetric molar concentration of alkali is about 0.0024mol/L) elutriant wash-out, 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 dry and be 95.2% product, Fig. 6 is shown in the battery characterization test of products obtained therefrom.
Embodiment 6
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, with acetonitrile: water: 10% TBAH=5L:1L:25mL(is that the volumetric molar concentration of alkali is about 0.0024mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～17cm and 11～1cm.Revolve and steam between the rear pH to 4.7 of adjusting.Freezing, filter, obtain purity after dry and be 96.4% product, Fig. 7 is shown in the battery characterization test of products obtained therefrom.
Embodiment 7
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, with methyl alcohol: water: 10% TBAH=5L:1L:21mL(is that the volumetric molar concentration of alkali is about 0.0020mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～17cm and 10～1cm.Revolve and steam between the rear pH to 5.4 of adjusting.Freezing, filter, obtain purity after dry and be 97.2% product, Fig. 8 is shown in the battery characterization test of products obtained therefrom.
Embodiment 8
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 cyano group (diameter 9cm, height 50cm), column chromatography after loading, with acetonitrile: water: 10% TBAH=4L:1L:17mL(is that the volumetric molar concentration of alkali is about 0.0016mol/L) elutriant wash-out, the flow velocity of pump is 21mL/min.During wash-out, collect the sample of 30～17cm and 13～1cm.Revolve and steam between the rear pH to 4.3 of adjusting.Freezing, filter, obtain purity after dry and be 93.6% product, the battery characterization test of products obtained therefrom.
Effect embodiment
The ruthenium complex dyestuff that embodiment 1～8 is obtained 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, form 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 consists of semiconductor nano-particles layers 7 and dye coating 6.Wherein, semiconductor nano-particles layers 7 is connected with conductive layer 5, and dye coating 6 is connected with dielectric substrate 3
Wherein, transparent substrates layer is glass coating, and conductive layer is FTO, and nanoparticle layers is TiO
2, dye coating 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 more than 7.24%, reaches as high as 7.82%.
Claims (9)
1. a method of utilizing column chromatography purification ruthenium complex dyestuff crude product, it comprises the steps:
Steps A) ruthenium complex dyestuff crude product is become to soluble salt with alkali reacting by heating in organic solvent, filter;
Step B) upper reverse chromatograms filled column;
Step C) with 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 steaming sample and remove organic solvent, add diluted acid acidizing crystal;
Step e) freezing its sufficient crystallising that makes, thaws, and filters, the dry ruthenium complex dye product that obtains;
Wherein, the structural formula of described ruthenium complex is suc as formula shown in (I),
Wherein, R
1, R
2for the group after heterocyclic radical, alkyl or heterocyclic radical and alkyl combination; R
3, R
4for carboxyl or phosphate;
Steps A) and step C) in, described organic solvent is methyl alcohol, ethanol or acetonitrile.
2. the method for claim 1, 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, 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, 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, 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), the 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 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) described in, be heated to be at 30～60 ℃ of heating 0.5～72h.
8. the method for claim 1, is characterized in that: step D), revolve steaming sample remove organic solvent in 20～60 ℃; 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; 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 to cleaning process; 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.
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