CN107312354A - A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method - Google Patents
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method Download PDFInfo
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- CN107312354A CN107312354A CN201710426522.1A CN201710426522A CN107312354A CN 107312354 A CN107312354 A CN 107312354A CN 201710426522 A CN201710426522 A CN 201710426522A CN 107312354 A CN107312354 A CN 107312354A
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- lycium ruthenicum
- pigment
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- petroleum ether
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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
- C09B61/00—Dyes of natural origin prepared from natural sources, e.g. vegetable sources
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0096—Purification; Precipitation; Filtration
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention discloses a kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method.Natural dye sensitizer lycium ruthenicum pigment is extracted, acylation reaction is then carried out to it, the number of OH groups in lycium ruthenicum pigment is reduced.By lycium ruthenicum drying and crushing, it is placed in absolute ethyl alcohol and centrifuges extract solution, repeatedly extracted using petroleum ether and distilled water, extract is concentrated in vacuo, pillar layer separation is carried out to concentrate, adds in caffeic acid and carry out acylation reaction.On the one hand the present invention improves the stability of plateau natural dye-sensitized solar cell by the lycium ruthenicum pigment of acylated modification; on the other hand the photoelectric transformation efficiency of battery is improved; and acylated modification is simple, it is easily-controllable the advantages of, have preferable market development prospect.
Description
Technical field
The present invention relates to a kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, belong to solar energy
Battery material preparing technical field.
Background technology
DSSC (Dye-sensitized solar cell, abbreviation DSC), is called " Gratzel " electricity
Pond, is a kind of new and effective sun of team's invention of the MGratzel professors of the federal science and engineering (EPFL) of Lausanne, SUI in 1991
Can battery.Not only manufacture craft is very simple, and need not the costliness high-temperature process of power consumption and high vacuum processing, therefore device again
The production cost of part is very cheap, it is estimated that be only 1/5 or so of silica-based solar cell.DSC theoretical conversion efficiencies are very high,
Up to 33%, more than the theoretical conversion efficiencies of monocrystalline silica-based solar cell.Based on above reason, DSC is also considered as thus
The contenders and replacer of traditional silicon based cells, increasing research heat is attract in Global Academy and industrial quarters
Feelings.
DSSC (DSC) is a kind of battery that simulating plant photosynthesis carries out opto-electronic conversion, wherein
Dye sensitizing agent is DSC key components, and it is adsorbed in nanoporous TiO2The particle of film, absorbs sunshine and produces light
Electronics, and photoelectron is injected into TiO2Conduction band in.Need have good absorption to sunshine as DSC dye sensitizing agent
Performance, with can be with TiO2Occur the group (such as hydroxyl, carboxyl, phosphate) of chemisorbed, can be to TiO2Inject electronics
And relatively good stability etc..Current people have synthesized nearly thousand kinds of dyestuffs, wherein with the bipyridyl complex of ruthenium
Preferably, but because its cost is higher, synthesis is difficult for photoelectric properties, and the large-scale of it is limited to a certain extent to be made
With.
Natural dye sensitizer is directly to be extracted from plant, obtain dyestuff process it is relatively easy, production cost compared with
It is low, and with it is environment-friendly, but natural dye sensitizer has certain deficiency as DSC dye sensitizing agent, causes day
The stability of right DSSC is undesirable, and photoelectric transformation efficiency is not high.
The content of the invention
It is an object of the invention to solve the problem of dye-sensitized dose of photoelectric transformation efficiency of existing lycium ruthenicum is low.Propose one
The extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method are planted, to improve lycium ruthenicum dye-sensitized solar electricity
The performance in pond.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, to the black Chinese holly of natural dye sensitizer
Qi pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2- OH the groups of light anode
Number, to reduce the compound of electric charge.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, it comprises the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 40-60 DEG C of drier and dries 120min, then crush,
Obtain black powder standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is put at room temperature after ultrasonic 25-35min
Put after 24h, centrifuge extract solution；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted using petroleum ether and distilled water,
Extract is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor are as eluant, eluent, polyamide dry column-packing,
Pillar layer separation is carried out to concentrate, dye-sensitized dose of lycium ruthenicum is obtained；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) prepare 1mol/L caffeic acid, then lycium ruthenicum pigment is added in caffeic acid configure, caffeic acid and
The volume ratio of lycium ruthenicum pigment is 1:1.5-3, anhydrous Aluminum chloride is as catalyst, while it is anti-to be to slowly warm up to 80 DEG C of progress water-baths
Should, 30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and many
After remaining caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：Will
TiO2Film is soaked in dyestuff after 24h at room temperature obtains light anode with the unnecessary dyestuff of the clean film surface of absolute ethyl alcohol,
Light anode and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery；
The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, particle diameter ＜ 1um is crushed to, by cell membrane
Smash completely.
The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:70-110, centrifugal rotational speed is during centrifugation
4000r/min。
When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 5-10 minute, then stand to layering, by underlying collection, then
Distilled water is with petroleum ether layer according to volume ratio 2-3:1 mixing is washed for 5-10 minutes, stands supreme lower leaf, and water system layer is received
Collection, then, until petroleum ether is mutually colourless, the dyestuff after extraction is carried out to low temperature under vacuo dense through row repeatedly extraction with petroleum ether
Contracting, vacuum is 7000pa, and temperature is 25-40 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
The concentrate that the step 4 is obtained tlc analysis on lamellae, mixture with petroleum ether and ether is as washing
De- agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum
Dyestuff.
The concentration of lycium ruthenicum ethanol pigment is 20-100mg/L in the step 6.
The present invention needs the lycium ruthenicum pigment being acylated to be the Anthocyanin class containing multiple-OH in molecular structure,
Its molecular structural formula is as follows：
By acylation reaction, remove partially away from TiO2Light anode-OH.
A kind of method of acylated lycium ruthenicum dye-sensitized solar cell of the present invention has have as follows compared with prior art
Beneficial effect：The present invention provides the method being acylated to the lycium ruthenicum pigment for DSSC first, with
Existing Natural dyestuff sensitizer on plateau is compared, and has the advantages that to improve plateau DSSC photoelectric properties.With
Existing synthetic dyestuffs are compared, simple and easy to apply with preparation method, react easily controllable, the features such as abundant raw material.So this hair
The bright method being acylated to plateau endemic plant lycium ruthenicum, has very heavy to the application of lycium ruthenicum dye-sensitized solar cell
The meaning wanted.In addition, the exploitation of plateau endemic plant can encourage the plantation plateau plant of Qinghai-Tibet peasants and herdsmen suitably again, it is it
One extra earning channel is provided, increases its job opportunity, with good economic benefit.
The lycium ruthenicum pigment for carrying out being acylated modification to it the need for of the present invention is the plant cyanine containing multiple-OH
Plain class, acylation reaction is carried out to lycium ruthenicum pigment, is reduced partially away from TiO2Light anode-OH so that lycium ruthenicum is dye-sensitized
The performance of solar cell is improved.The present invention makes full use of Qinghai-Tibet height above sea level, the geography of ultraviolet irradiation time length
Feature, chooses the Qinghai-Tibet plant endemic plant lycium ruthenicum containing anthocyanidin, therefrom extracts for dye sensitization of solar electricity
The lycium ruthenicum pigment of pond sensitizer, and it is carried out to be acylated modification.This lycium ruthenicum pigment for being acylated modification excessively is on the one hand
The stability of plateau natural dye-sensitized solar cell is improved, the photoelectric transformation efficiency of battery is on the other hand improved, and
And acylated modification it is simple, it is easily-controllable the advantages of, have preferable market development prospect.
Embodiment
With reference to embodiment to a kind of method and technology scheme of acylated lycium ruthenicum dye-sensitized solar cell of the present invention
It is further described.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, to the black Chinese holly of natural dye sensitizer
Qi pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2- OH the groups of light anode
Number, to reduce the compound of electric charge.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, it comprises the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 40-60 DEG C of drier and dries 120min, then crush,
Obtain black powder standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is put at room temperature after ultrasonic 25-35min
Put after 24h, centrifuge extract solution；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted using petroleum ether and distilled water,
Extract is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor are as eluant, eluent, polyamide dry column-packing,
Pillar layer separation is carried out to concentrate, dye-sensitized dose of lycium ruthenicum is obtained；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) prepare 1mol/L caffeic acid, then lycium ruthenicum pigment is added in caffeic acid configure, caffeic acid and
The volume ratio of lycium ruthenicum pigment is 1:1.5-3, anhydrous Aluminum chloride is as catalyst, while it is anti-to be to slowly warm up to 80 DEG C of progress water-baths
Should, 30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and many
After remaining caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：Will
TiO2Film is soaked in dyestuff after 24h at room temperature obtains light anode with the unnecessary dyestuff of the clean film surface of absolute ethyl alcohol,
Light anode and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery；
The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, particle diameter ＜ 1um is crushed to, by cell membrane
Smash completely.
The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:70-110, centrifugal rotational speed is during centrifugation
4000r/min。
When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 5-10 minute, then stand to layering, by underlying collection, then
Distilled water is with petroleum ether layer according to volume ratio 2-3:1 mixing is washed for 5-10 minutes, stands supreme lower leaf, and water system layer is received
Collection, then, until petroleum ether is mutually colourless, the dyestuff after extraction is carried out to low temperature under vacuo dense through row repeatedly extraction with petroleum ether
Contracting, vacuum is 7000pa, and temperature is 25-40 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
The concentrate that the step 4 is obtained tlc analysis on lamellae, mixture with petroleum ether and ether is as washing
De- agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum
Dyestuff.
The concentration of lycium ruthenicum ethanol pigment is 20-100mg/L in the step 6.
Embodiment 1
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, to the black Chinese holly of natural dye sensitizer
Qi pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2- OH the groups of light anode
Number, to reduce the compound of electric charge.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, it comprises the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 45 DEG C of drier and dries 120min, then crush, obtain
Black powder is standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is placed at room temperature after ultrasonic 33min
After 24h, extract solution is centrifuged；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted using petroleum ether and distilled water,
Extract is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor are as eluant, eluent, polyamide dry column-packing,
Pillar layer separation is carried out to concentrate, dye-sensitized dose of lycium ruthenicum is obtained；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) prepare 1mol/L caffeic acid, then lycium ruthenicum pigment is added in caffeic acid configure, caffeic acid and
The volume ratio of lycium ruthenicum pigment is 1:1.8, anhydrous Aluminum chloride is as catalyst, while it is anti-to be to slowly warm up to 80 DEG C of progress water-baths
Should, 30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and many
After remaining caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：Will
TiO2Film is soaked in dyestuff after 24h at room temperature obtains light anode with the unnecessary dyestuff of the clean film surface of absolute ethyl alcohol,
Light anode and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery；
The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, particle diameter ＜ 1um is crushed to, by cell membrane
Smash completely.
The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:85, centrifugal rotational speed is 4000r/ during centrifugation
min。
When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 8 minutes, then stand to being layered, then underlying collection distills
Water is with petroleum ether layer according to volume ratio 2.3:1 mixing is washed for 8 minutes, stands supreme lower leaf, and water system layer is collected, then uses
Dyestuff after extraction, until petroleum ether is mutually colourless, is carried out low temperature concentration, vacuum by petroleum ether under vacuo through row repeatedly extraction
For 7000pa, temperature is 35 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
The concentrate that the step 4 is obtained tlc analysis on lamellae, mixture with petroleum ether and ether is as washing
De- agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum
Dyestuff.
The concentration of lycium ruthenicum ethanol pigment is 80mg/L in the step 6.
Embodiment 2
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, to the black Chinese holly of natural dye sensitizer
Qi pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2- OH the groups of light anode
Number, to reduce the compound of electric charge.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, it comprises the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 50 DEG C of drier and dries 120min, then crush, obtain
Black powder is standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is placed at room temperature after ultrasonic 32min
After 24h, extract solution is centrifuged；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted using petroleum ether and distilled water,
Extract is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor are as eluant, eluent, polyamide dry column-packing,
Pillar layer separation is carried out to concentrate, dye-sensitized dose of lycium ruthenicum is obtained；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) prepare 1mol/L caffeic acid, then lycium ruthenicum pigment is added in caffeic acid configure, caffeic acid and
The volume ratio of lycium ruthenicum pigment is 1:1.9, anhydrous Aluminum chloride is as catalyst, while it is anti-to be to slowly warm up to 80 DEG C of progress water-baths
Should, 30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and many
After remaining caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：Will
TiO2Film is soaked in dyestuff after 24h at room temperature obtains light anode with the unnecessary dyestuff of the clean film surface of absolute ethyl alcohol,
Light anode and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery；
The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, particle diameter ＜ 1um is crushed to, by cell membrane
Smash completely.
The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:100, centrifugal rotational speed is 4000r/ during centrifugation
min。
When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 8 minutes, then stand to being layered, then underlying collection distills
Water is with petroleum ether layer according to volume ratio 2.8:1 mixing is washed for 8 minutes, stands supreme lower leaf, and water system layer is collected, then uses
Dyestuff after extraction, until petroleum ether is mutually colourless, is carried out low temperature concentration, vacuum by petroleum ether under vacuo through row repeatedly extraction
For 7000pa, temperature is 35 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
The concentrate that the step 4 is obtained tlc analysis on lamellae, mixture with petroleum ether and ether is as washing
De- agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum
Dyestuff.
The concentration of lycium ruthenicum ethanol pigment is 85mg/L in the step 6.
Embodiment 3
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, to the black Chinese holly of natural dye sensitizer
Qi pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2- OH the groups of light anode
Number, to reduce the compound of electric charge.
A kind of extraction of natural dye sensitizer lycium ruthenicum pigment and its acylated method, it comprises the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 52 DEG C of drier and dries 120min, then crush, obtain
Black powder is standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is placed at room temperature after ultrasonic 32min
After 24h, extract solution is centrifuged；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted using petroleum ether and distilled water,
Extract is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor are as eluant, eluent, polyamide dry column-packing,
Pillar layer separation is carried out to concentrate, dye-sensitized dose of lycium ruthenicum is obtained；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) prepare 1mol/L caffeic acid, then lycium ruthenicum pigment is added in caffeic acid configure, caffeic acid and
The volume ratio of lycium ruthenicum pigment is 1:2.8, anhydrous Aluminum chloride is as catalyst, while it is anti-to be to slowly warm up to 80 DEG C of progress water-baths
Should, 30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and many
After remaining caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：Will
TiO2Film is soaked in dyestuff after 24h at room temperature obtains light anode with the unnecessary dyestuff of the clean film surface of absolute ethyl alcohol,
Light anode and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery；
The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, particle diameter ＜ 1um is crushed to, by cell membrane
Smash completely.
The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:105, centrifugal rotational speed is 4000r/ during centrifugation
min。
When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 5-10 minute, then stand to layering, by underlying collection, then
Distilled water is with petroleum ether layer according to volume ratio 2.1:1 mixing is washed for 9 minutes, stands supreme lower leaf, and water system layer is collected,
, until petroleum ether is mutually colourless, the dyestuff after extraction is subjected to low temperature concentration under vacuo, very through row repeatedly extraction with petroleum ether again
Reciprocal of duty cycle is 7000pa, and temperature is 25-40 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
The concentrate that the step 4 is obtained tlc analysis on lamellae, mixture with petroleum ether and ether is as washing
De- agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum
Dyestuff.
The concentration of lycium ruthenicum ethanol pigment is 85mg/L in the step 6.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to skill of the invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (7)
1. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment, it is characterised in that to natural dye
Sensitizer lycium ruthenicum pigment is extracted, and acylation reaction is then carried out to it, is reduced in lycium ruthenicum pigment away from TiO2Light anode
- OH groups number, to reduce the compound of electric charge.
2. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 1, it is special
Levy and be, comprise the following steps：
1) by lycium ruthenicum clear water clean dry, it is placed in 40-60 DEG C of drier and dries 120min, then crush, obtain
Black powder is standby；
2) by step 1) obtained black powder is placed in absolute ethyl alcohol, and shading is placed at room temperature after ultrasonic 25-35min
After 24h, extract solution is centrifuged；
3) by step 2) obtained lycium ruthenicum pigment centrifuge the extract, repeatedly extracted, extracted using petroleum ether and distilled water
Liquid is concentrated in vacuo；
4) using step 3) obtained concentrate petroleum ether and ether mixed liquor be used as eluant, eluent, polyamide dry column-packing, to dense
Contracting liquid carries out pillar layer separation, obtains dye-sensitized dose of lycium ruthenicum；
5) by step 4) dye-sensitized dose of lycium ruthenicum being obtained using pillar layer separation carries out spin concentration at 45 DEG C；
6) 1mol/L caffeic acid is prepared, is then added to lycium ruthenicum pigment in the caffeic acid configured, caffeic acid and black Chinese holly
The volume ratio of Qi pigment is 1:1.5-3, anhydrous Aluminum chloride is as catalyst, while 80 DEG C of progress water-baths are to slowly warm up to,
30min is reacted, acylation reaction is completed；
7) system is added in round-bottomed flask after the completion of reacting, spin concentration is carried out at 45 DEG C, solvent is removed and unnecessary
After caffeic acid, that is, the lycium ruthenicum pigment after being acylated, round-bottomed flask reclaims the caffeic acid after revolving；
8) using the lycium ruthenicum dye-sensitized solar cell after being acylated, and photoelectric properties test is carried out.It is prepared by battery：By TiO2
Film is soaked in dyestuff after 24h at room temperature obtains light anode, light sun with the dyestuff that it is unnecessary that absolute ethyl alcohol cleans film surface
Pole and to electrode with flat mouth it is clamping it is fixed assembling " sandwich " structure battery, carry out photoelectric properties test.
3. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 2, it is special
Levy and be：The lycium ruthenicum harvesting is from Qinghai-Tibet Platean, and drier is air dry oven, is crushed to particle diameter ＜ 1um, and cell membrane is complete
Smash entirely.
4. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 2, it is special
Levy and be：The mass ratio of step 2 black powder and absolute ethyl alcohol is 1:70-110, centrifugal rotational speed is during centrifugation
4000r/min。
5. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 2, it is special
Levy and be：When the step 3 petrochina ether and distilled water are extracted, using the method repeatedly extracted on a small quantity, first by petroleum ether
With centrifuge the extract according to volume ratio 1:3 carry out concussion mixing 5-10 minute, then stand to layering, by underlying collection, then
Distilled water is with petroleum ether layer according to volume ratio 2-3:1 mixing is washed for 5-10 minutes, stands supreme lower leaf, and water system layer is received
Collection, then, until petroleum ether is mutually colourless, the dyestuff after extraction is carried out to low temperature under vacuo dense through row repeatedly extraction with petroleum ether
Contracting, vacuum is 7000pa, and temperature is 25-40 DEG C, and it is the 1/3 of initial volume to be concentrated into volume.
6. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 2, it is special
Levy and be：The concentrate that the step 4 is obtained tlc analysis on lamellae, elution is used as with the mixture of petroleum ether and ether
Agent, petroleum ether:The volume ratio 5 of ether:2, polyamide dry column-packing carries out pillar layer separation to concentrate, obtains lycium ruthenicum dye
Material.
7. extraction and its acylated method of a kind of natural dye sensitizer lycium ruthenicum pigment as claimed in claim 2, it is special
Levy and be：The concentration of lycium ruthenicum ethanol pigment is 20-100mg/L in the step 6.
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