CN105859729A - Porphyrin small organic molecule cathode interface material and preparation method thereof - Google Patents
Porphyrin small organic molecule cathode interface material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porphyrin small organic molecule cathode interface material. A porphyrin ring is adopted as the core, four meso-positions of the porphyrin ring are each connected with a group, wherein two meso-positions are conjugated units with polar groups, and two meso-positions are aromatic substituent groups. The invention further discloses a preparation method of the porphyrin small organic molecule cathode interface material. Pyrrole is adopted as the original reaction raw material, a series of reactions are conducted, and finally coupling with the different conjugation units with the polar groups is conducted through palladium catalysis, so that the porphyrin small organic molecule cathode interface material is obtained. Compared with the prior art, pi-pi accumulation among molecules of the porphyrin small organic molecule cathode interface material in the film formation state is improved, and furthermore electronic transmission performance is improved; the dissolving property of the material in methyl alcohol is improved, and by means of the material, photoelectric conversion efficiency of a solar cell can be further improved.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly to a kind of porphyrin organic molecule cathode interface material and preparation method thereof.
Background technology
Along with socioeconomic development, energy-output ratio is increasing, and traditional fossil energy is the most exhausted, and exploitation regenerative resource has become the important subject of current researcher.Solar energy is a kind of reproducible clean energy resource, possesses the advantages such as reserves are big, distribution is wide, is a huge energy treasure-house, and the exploitation of solar energy have become as the focus of various countries' extensive concern.Utilize photovoltaic cell to convert the solar into electric energy and become one of most effective technology utilizing solar energy.
The photovoltaic cell of the comparative maturity of the research that initial development is got up is based on inorganic material, although have been commercialized, but because its processing cost is high, application is limited by very large.Comparatively speaking, the organic polymer of solution-processible and organic small molecule material solar cell have the features such as low cost, easily processing (as can spin coating, inkjet printing etc.), and it is lightweight, possesses potential advantages such as making large area flexible device, can well overcome the defect of inorganic photovoltaic cell, thus of great interest.
Organic photovoltaic battery structure is relatively simple, will constitute between electrodes by light active material folder, and one of them electrode is transparent, and beneficially light transmission electrode is absorbed by active layer, and then carries out opto-electronic conversion.In order to obtain higher photoelectric transformation efficiency, typically can insert a bed boundary material between electrode and active layer, it is divided into anodic interface material and cathode interface material, for cathode interface, the most most widely used is the molten polymeric material of water/alcohol, the easy film forming of this base polymer, but it is not easy to purify, molecular weight distribution width, the product that every batch is synthesized causes the efficiency of solar cell to be usually present difference owing to molecular weight and distribution thereof there are differences, and there are not these problems in organic molecule, therefore there is the advantage of its uniqueness in organic molecule in organic solar batteries.
Porphyrin is to be obtained by the method such as extracting and developing, purifying from the natural products containing porphyrin compound, its structure is similar with chlorophyll, there is big pi-conjugated system, be conducive to electric transmission, and the modification easily by peripheral groups and cavity metal changes its physicochemical properties, Porphyrin and its derivative is high because of its molar extinction coefficient, typically can be used as active layer in photovoltaic device.Porphyrin has been used in cathode interface the most gradually in recent years, but there are some characteristics such as structural rigidity due to it, it is difficult to dissolve in polar solvent, there are some problems when as boundary material, porphyrin is modified by some researchers afterwards, improves its dissolubility in polar solvent, only drawback is that, up to the present, porphyrin material does not play extraordinary modifying interface effect.
Summary of the invention
In order to overcome the disadvantages mentioned above of prior art with not enough, it is an object of the invention to provide a kind of porphyrin organic molecule cathode interface material, by porphyrin is modified so that it is have extraordinary dissolubility in polar solvent, effectively increase the electronic transmission performance of organic electro-optic device.
Another object of the present invention is to provide the preparation method of a kind of porphyrin organic molecule cathode interface material.
The purpose of the present invention is achieved through the following technical solutions: a kind of porphyrin organic molecule cathode interface material, has a following chemical constitution:
Wherein, A is the conjugate unit with polar group；M is metal ion or protium；Ar is aromatic substituent group；
A is the one in following construction unit:
Wherein, R is containing the alkyl with polar group that carbon number is 0 to 20 or oxyalkyl chain.
Described polar group has an one in following structure: amido, diethanol amido, phosphate-based, carboxyl, quaternary ammonium salt, carboxylate radical, sulfonate radical, amphion group.
Described M is zinc ion, copper ion, magnesium ion, nickel ion or hydrogen ion.
Described Ar has an one in following construction unit:
Wherein, R1It is containing the alkyl that carbon number is 0 to 20 or alkoxyl.
The preparation method of described porphyrin organic molecule cathode interface material, comprises the following steps:
Suzuki coupling reaction is used to prepare: under an argon atmosphere by 5, the double borate porphyrin of 10-, bromide are dissolved in and fill 1, in the reaction bulb of 2-dimethoxy-ethane, add four (triphenyl phosphorus) and close palladium, add aqueous slkali, add thermal agitation reaction, after cooling, extract target product with chloroform, purified by silica gel column chromatography and GPC, finally being spin-dried for solvent, product is dried under vacuum, and obtains porphyrin organic molecule cathode interface material；
The mole of described bromide is 5,3～6 times of the mole of the double borate porphyrin of 10-, described 1, the mole of 2-dimethoxy-ethane is 5, the double borate porphyrin of 10-and 45～55 times of bromide integral molar quantity, described four (triphenyl phosphorus) closes the mole of palladium is 5, the 8～12% of the double borate porphyrin mole of 10-.
The preparation method of described porphyrin organic molecule cathode interface material, comprises the following steps:
Sonogashira coupling reaction is used to prepare: under an argon atmosphere by 5, the double ethynyl porphyrins of 10-, bromide are dissolved in the reaction bulb filling toluene and triethylamine, add four (triphenyl phosphorus) and close palladium and cuprous iodide, add thermal agitation reaction, after cooling, extract target product with chloroform, purified by silica gel column chromatography, finally being spin-dried for solvent, product is dried under vacuum, and obtains porphyrin organic molecule cathode interface material；
The mole of described bromide is 5,3～6 times of the mole of the double ethynyl porphyrins of 10-, the mole of described toluene is 5, the double ethynyl porphyrins of 10-and 45～55 times of bromide integral molar quantity, described triethylamine is 1/3rd of toluene amount, and described four (triphenyl phosphorus) closes the mole of palladium is 5, the 8～12% of the double ethynyl porphyrins mole of 10-, the mole of described cuprous iodide is 5, the 8～12% of the double ethynyl porphyrins mole of 10-.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the porphyrin organic molecule cathode interface material of the present invention is with porphyrin as core, by connecting other conjugation groups, effectively increases pi-conjugated system and the electron transport ability of molecule；Simultaneously by connecting polar group and other side chains so that molecule has extraordinary water/alcohol-soluble.
(2) the porphyrin organic molecule cathode interface material of the present invention is by introducing different metal ions in the cavity of porphyrin, owing to different metal ions has different outer shell electron distributions and to-electron-withdrawing power, the regulation HOMO of synthetic material, lumo energy further, make this boundary material can effectively reduce the work content of metal electrode, improve the photoelectric transformation efficiency of photovoltaic device further.
(3) the porphyrin organic molecule cathode interface material extinction of the present invention is narrower, and it is partially blue, when using this material, interface has good photopermeability so that sunshine is absorbed by active layer to greatest extent, thus improves the photoelectric transformation efficiency of photovoltaic device further.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra of the dichloromethane solution of embodiments of the invention 1,2.
Fig. 2 is the porphyrin organic molecule boundary material of embodiments of the invention 1,2 uv-visible absorption spectra under filminess.
The photovoltaic cell of Fig. 3 embodiments of the invention 1,2 preparation is at AM 1.5,100mW/cm2Current-voltage curve figure under illumination.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The synthesis of (1) 5,15-double (3,4-double (3,6-dioxoethyl methyl) benzene) porphyrin
In 500mL three neck round bottom flask, add 3,4-double (3,6-dioxoethyl methyl) benzaldehyde (1.19g, 3.48mmol), dipyrromethane (508mg, 3.48mmol) and the dichloromethane of 350mL, ventilate 30 minutes with nitrogen, be subsequently adding the trifluoroacetic acid of 0.035mL, it is stirred at room temperature reaction 12 hours, add 1.18g 2,3-bis-chloro-5,6-dicyano-1,4-benzoquinones (DDQ), continues stirring reaction 12 hours.After reaction terminates, with silica gel/(dichloromethane is eluant, eluent) column chromatography, obtain crude product after being spin-dried for, then recrystallize by chloroform/methanol, obtain dark red solid.1H NMR (500MHz, CDCl3null): δ 10.30 (s，2H)，9.38(d，J=4.6Hz，4H)，9.11(d，J=4.6Hz，4H)，7.87(t，J=1.7Hz，2H)，7.79(d，J=8.1Hz，2H)，7.34(d，J=8.1Hz，2H)，4.51(dd，J=5.7，4.5Hz，4H)，4.40-4.34(m，4H)，4.11(dd，J=5.7，4.5Hz，4H)，3.99-3.94(m，4H)，3.93-3.88(m，4H)，3.80-3.74(m，4H)，3.72-3.66(m，4H)，3.57-3.51(m，4H)，3.49(s，6H)，3.29(s，6H)，-3.10(s，2H).
The synthesis of (2) 5,15-double bromo-10,20-double (3,4-double (3,6-dioxoethyl methyl) benzene) zinc protoporphyrin
By 5,15-double (3,4-double (3,6-dioxoethyl methyl) benzene) porphyrin (500mg, 0.54mmol) it is dissolved in the chloroform of 250mL, add the pyridine of 2.5mL, after lucifuge is fully dissolved, be subsequently adding bromo-succinimide (NBS) (211mg, 1.19mmol), 0 DEG C react 30 minutes, after at room temperature continue reaction overnight, finally with acetone cancellation react.React complete, add water, extract with chloroform, anhydrous sodium sulfate is dried, and is dissolved in the chloroformic solution of 50mL after being spin-dried for solvent, the rear zinc acetate methanol solution (273mg adding 10mL, the zinc acetate of 1.35mmol is dissolved in the methanol solvate of 10mL), lucifuge refluxes 2 hours.React complete, washing, and be dried with anhydrous sodium sulfate, it is spin-dried for solvent, uses silica gel column chromatography to obtain the solid of shiny red after purification.1H NMR (500MHz, CDCl3): δ 9.69 (d, J=4.5Hz, 4H), 8.95 (d, J=4.5Hz, 4H), 7.68 (d, J=5.9Hz, 2H), 7.63 (t, J=7.3Hz, 2H), 7.12 (dd, J=11.4,8.0Hz, 2H), 4.24 (d, J=6.0Hz, 4H), 4.10 (d, J=21.8Hz, 4H), 3.76 (t, J=5.0Hz, 4H), 3.70-3.53 (m, 8H), 3.50-3.36 (m, 8H), 3.32-3.16 (m, 10H), (3.07 d, J=21.6Hz, 6H).
Double (trimethylsilyl acetylene)-10 of (3) 5,15-, the synthesis of 20-double (3,4-double (3,6-dioxoethyl methyl) benzene) zinc protoporphyrin
In two mouthfuls of round-bottomed flasks of 100mL, add 5,15-double bromo-10,20-double (3, double (dodecyloxy) benzene of 5-) zinc protoporphyrin (400mg, 0.346mmol), 40mL oxolane and 20mL triethylamine, logical nitrogen 30 minutes, it is subsequently adding double (triphenylphosphine) palladium chloride (25mg, 0.036mmol), cuprous iodide (CuI) (7.05mg, 0.036mmol) and trimethylsilyl acetylene (169mg, 1.73mmol), lucifuge, reaction is stirred at room temperature reaction three days.React complete, with chloroform extraction, washing, be dried with anhydrous sodium sulfate, recycle silicon glue/(methylene chloride/methanol=30/1 is eluant, eluent) column chromatography, be spin-dried for obtaining the solid of green.1H NMR (500MHz, CDCl3null): δ 9.69 (dd，J=4.6，1.6Hz，4H)，8.93(dd，J=4.5，1.5Hz，4H)，7.70(dd，J=6.5，2.0Hz，2H)，7.65(m，2H)，7.14(dd，J=11.5，8.0Hz，2H)，4.32-4.22(m，4H)，4.15(d，J=22.1Hz，4H)，3.83(d，J=6.6Hz，4H)，3.71(d，J=29.2Hz，4H)，3.61-3.64(m，4H)，3.53-3.40(m，8H)，3.33-3.21(m，10H)，3.11(d，J=20.1Hz，6H)，0.62(s，18H).
Double (acetylene)-10 of (4) 5,15-, the synthesis of 20-double (3,4-double (3,6-dioxoethyl methyl) benzene) zinc protoporphyrin
By 5, double (trimethylsilyl acetylene)-10 of 15-, 20-double (3, double (dodecyloxy) benzene of 5-) zinc protoporphyrin (165mg, 0.14mmol) it is dissolved in the tetrahydrofuran solution of 20mL, adds tetrabutyl ammonium fluoride (0.3mL, 1M in THF), being stirred at room temperature reaction 5 minutes, the cancellation that adds water is reacted.Extracting with chloroform, anhydrous sodium sulfate is dried, and is spin-dried for, and by gel column separation impurity, is spin-dried for obtaining the solid of green.1H NMR (500MHz, CDCl3): δ 9.71 (dd, J=4.7,1.2Hz, 4H), 8.96 (dd, J=4.6,1.1Hz, 4H), 7.73 (t, J=2.6Hz, 2H), 7.67 (dd, J=7.8,2.9Hz, 2H), 7.19 (t, J=7.2Hz, 2H), 4.35 (s, 4H), 4.18 (d, J=9.4Hz, 4H), 3.91 (d, J=9.9Hz, 4H), 3.76 (d, J=31.8Hz, 8H), 3.56 (d, J=26.9Hz, 8H), 3.39-3.31 (m, 12H), 3.16 (d, J=13.5Hz, 6H).
(5) 2-bromo-9, the synthesis of 9-bis-(3 '-(N, N-dimethyl amido) propyl group) fluorenes
Under the protection of argon gas; by 2-bromine fluorenes (2.94g; 12mmol) it is dissolved in 60ml dimethyl sulfoxide (DMSO), adds 80mg TBAB, be subsequently added into 8ml sodium hydroxide solution (50wt%); after stirring a little while; 3-(N, N-dimethyl) amino-n-propyl chloride hydrochloride (5g, 32mmol) is dissolved in 20mlDMSO; it is added drop-wise in this system, after adding, at room temperature continues reaction 6h.Reacting addition 50ml water after terminating, with the salt in dissolution system, to extract with ether, successively with sodium hydroxide solution, water, saturated aqueous common salt washs, and anhydrous magnesium sulfate is dried, and is spin-dried for, and repeatedly recrystallizes to obtain white solid, and room temperature is viscous liquid.1H NMR (500MHz, DMSO-d6): δ 7.67-7.63 (m, 1H), 7.54 (d, J=8.1Hz, 1H), 7.48 (d, J=1.8Hz, 1H), 7.44 (dd, J=8.0,1.8Hz, 1H), 7.36-7.28 (m, 3H), 2.08-1.92 (m, 20H), 0.84-0.68 (m, 4H).
Double (9,9-bis-(3 '-(N, the N-dimethyl amido) propyl group) fluorenes-2-acetylene)-10 of (6) 5,15-, the synthesis of 20-double (3,4-double (3,6-dioxoethyl methyl) benzene) zinc protoporphyrin
Under the protection of argon gas, 5 are added in two mouthfuls of round-bottomed flasks of 50mL, double (acetylene)-10 of 15-, 20-double (3, 4-double (3, 6-dioxoethyl methyl) benzene) zinc protoporphyrin (133mg, 0.13mmol), 2-bromo-9, 9-bis-(3 '-(N, N-dimethyl amido) propyl group) fluorenes (158mg, 0.38mmol), dry toluene (20mL), triethylamine (10mL), cuprous iodide (2.5mg, 0.01mmol) with tetrakis triphenylphosphine palladium (14.6mg, 0.01mmol), reaction system lucifuge, stirring reaction three days at 80 DEG C.React complete, it is cooled to room temperature, add water quencher, extracts with chloroform, washing, anhydrous sodium sulfate is dried, it is spin-dried for, crosses silicagel column separation crude product (eluant, eluent: methylene chloride/methanol/triethylamine=10/1/0.5), then with gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (oxolane is eluant, eluent), obtains cyan solid.Mass (MALDI-TOF): Obs.1713.6；Calcd.for C102H120N8O12Zn, 1712.8.
The porphyrin organic molecule boundary material prepared by the present embodiment is dissolved in dichloromethane, and the uv-visible absorption spectra of the dichloromethane solution obtained is shown in Fig. 1.
The porphyrin organic molecule boundary material prepared by the present embodiment is prepared as film, and its uv-visible absorption spectra is shown in Fig. 2.
Utilize photovoltaic cell prepared by the porphyrin organic molecule boundary material of the present embodiment at AM 1.5,100mW/cm2Current-voltage curve under illumination is shown in Fig. 3, device architecture: ITO/PEDOT:PSS/PTB7:PC71BM/ interface/Al.Figure gives the battery without cathode interface layer simultaneously and uses typical cathodic boundary material poly [(9,9-bis (3 '-(N, N-dimethylamino) propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) is the battery of cathodic modification layer, to compare.
Embodiment 2
5,15-double (9,9-bis-(3 '-(N, N-dimethyl amido) propyl group) fluorenes)-10, the synthesis of double (3, the 5-di-tert-butyl-phenyl) zinc protoporphyrin of 20-
nullUnder the protection of argon gas，5 are added in the single necked round bottom flask of 25mL，15-double (4，4，5，5-tetramethyl-1，3，2-di (hetero) oxygen pentaborane)-10，20-double (3，5-dual-tert-butyl benzene) zinc protoporphyrin (40mg，0.04mmol)，2-bromo-9，9-bis-(3 '-(N，N-dimethyl amido) propyl group) fluorenes (50mg，0.12mmol)，Barium hydroxide octahydrate (27mg，0.08mmol)，Tetrakis triphenylphosphine palladium (9.6mg，0.008mmol)，1 just steamed，2-dimethoxy-ethane (3mL) and water (0.1mL)，After carry out freezing-pump-thaw (freeze-pump-thaw) and circulate the oxygen in three removing systems，It is passed through argon gas again，Lucifuge，And stirring is reacted 72 hours at 90 DEG C.React complete, it is cooled to room temperature, add water quencher, extracting with chloroform, washing, anhydrous sodium sulfate is dried, it is spin-dried for, cross silicagel column separation crude product (eluant, eluent: methylene chloride/methanol/triethylamine=100/1/1), then with gel permeation chromatography (GPC) column chromatography (oxolane is eluant, eluent), obtain mauve solid.Mass (MALDI-TOF): Obs.1417.8；Calcd.for C94H112N8Zn, 1416.8.
The porphyrin organic molecule boundary material prepared by the present embodiment is dissolved in dichloromethane, and the uv-visible absorption spectra of the dichloromethane solution obtained is shown in Fig. 1.
The porphyrin organic molecule boundary material prepared by the present embodiment is prepared as film, and its uv-visible absorption spectra is shown in Fig. 2.
Utilize photovoltaic cell prepared by the porphyrin organic molecule boundary material of the present embodiment at AM 1.5,100mW/cm2Current-voltage curve under illumination is shown in Fig. 3, device architecture: ITO/PEDOT:PSS/PTB7:PC71BM/ interface/Al.
Embodiment 3
5,15-double (9,9-bis-(3 '-(N, N-dimethyl amido) propyl group) fluorenes)-10, the synthesis of 20-double (3,4-double (3,6-dioxoethyl methyl) benzene) zinc protoporphyrin
nullUnder the protection of argon gas，5 are added in the single necked round bottom flask of 25mL，15-double (4，4，5，5-tetramethyl-1，3，2-di (hetero) oxygen pentaborane)-10，20-double (3，4-double (3，6-dioxoethyl methyl) benzene) zinc protoporphyrin (41mg，0.04mmol)，2-bromo-9，9-bis-(3 '-(N，N-dimethyl amido) propyl group) fluorenes (50mg，0.12mmol)，Barium hydroxide octahydrate (27mg，0.08mmol)，Tetrakis triphenylphosphine palladium (9.6mg，0.008mmol)，1 just steamed，2-dimethoxy-ethane (3mL) and water (0.1mL)，After carry out freezing-pump-thaw (freeze-pump-thaw) and circulate the oxygen in three removing systems，It is passed through argon gas again，Lucifuge，And stirring is reacted 72 hours at 90 DEG C.React complete, it is cooled to room temperature, add water quencher, extracts with chloroform, washing, anhydrous sodium sulfate is dried, it is spin-dried for, crosses silicagel column separation crude product (eluant, eluent: methylene chloride/methanol/triethylamine=100/1/1), then with gel permeation chromatography (Gel Permeation Chromatography, GPC) column chromatography (oxolane is eluant, eluent), obtains mauve solid.Mass (MALDI-TOF): Calcd.for C98H120N8O12Zn, 1667.4, Obs.1667.8.
In the little following chemical constitution of molecular interface material of the present invention:
A can be also other conjugate units, and its polar group connected also has a variety of, M can also be copper ion, magnesium ion, nickel ion etc., and Ar can be also other aromatic substituent groups, its preparation principle and performance are similar with the embodiment that the present invention is given, and no longer add at this to tell about.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted by the embodiments; the change made under other any Spirit Essence without departing from the present invention and principle, modify, substitute, combine, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (6)
1. a porphyrin organic molecule cathode interface material, it is characterised in that there is following chemical constitution:
Wherein, A is the conjugate unit with polar group；M is metal ion or protium；Ar is aromatic substituent group；
A is the one in following construction unit:
Wherein, R is containing the alkyl with polar group that carbon number is 0 to 20 or oxyalkyl chain.
Porphyrin organic molecule cathode interface material the most according to claim 1, it is characterized in that, described polar group has an one in following structure: amido, diethanol amido, phosphate-based, carboxyl, quaternary ammonium salt, carboxylate radical, sulfonate radical, amphion group.
Porphyrin organic molecule cathode interface material the most according to claim 1, it is characterised in that described M is zinc ion, copper ion, magnesium ion, nickel ion or hydrogen ion.
Porphyrin organic molecule cathode interface material the most according to claim 1, it is characterised in that
Described Ar has an one in following construction unit:
Wherein, R1It is containing the alkyl that carbon number is 0 to 20 or alkoxyl.
5. the preparation method of the porphyrin organic molecule cathode interface material described in any one of Claims 1 to 4, it is characterised in that comprise the following steps:
Suzuki coupling reaction is used to prepare: under an argon atmosphere by 5, the double borate porphyrin of 10-, bromide are dissolved in and fill 1, in the reaction bulb of 2-dimethoxy-ethane, add four (triphenyl phosphorus) and close palladium, add aqueous slkali, add thermal agitation reaction, after cooling, extract target product with chloroform, purified by silica gel column chromatography and GPC, finally being spin-dried for solvent, product is dried under vacuum, and obtains porphyrin organic molecule cathode interface material；
The mole of described bromide is 5,3～6 times of the mole of the double borate porphyrin of 10-, described 1, the mole of 2-dimethoxy-ethane is 5, the double borate porphyrin of 10-and 45～55 times of bromide integral molar quantity, described four (triphenyl phosphorus) closes the mole of palladium is 5, the 8～12% of the double borate porphyrin mole of 10-.
6. the preparation method of the porphyrin organic molecule cathode interface material described in any one of Claims 1 to 4, it is characterised in that comprise the following steps:
Sonogashira coupling reaction is used to prepare: under an argon atmosphere by 5, the double ethynyl porphyrins of 10-, bromide are dissolved in the reaction bulb filling toluene and triethylamine, add four (triphenyl phosphorus) and close palladium and cuprous iodide, add thermal agitation reaction, after cooling, extract target product with chloroform, purified by silica gel column chromatography, finally being spin-dried for solvent, product is dried under vacuum, and obtains porphyrin organic molecule cathode interface material；
The mole of described bromide is 5,3～6 times of the mole of the double ethynyl porphyrins of 10-, the mole of described toluene is 5, the double ethynyl porphyrins of 10-and 45～55 times of bromide integral molar quantity, described triethylamine is 1/3rd of toluene amount, and described four (triphenyl phosphorus) closes the mole of palladium is 5, the 8～12% of the double ethynyl porphyrins mole of 10-, the mole of described cuprous iodide is 5, the 8～12% of the double ethynyl porphyrins mole of 10-.
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| CN108516978A (en) * | 2018-04-04 | 2018-09-11 | 华南理工大学 | A kind of asymmetrical porphyrin organic molecule cathode interface material and its preparation method and application |
| CN109939735A (en) * | 2017-12-20 | 2019-06-28 | 湖南科技大学 | A kind of phase transfer catalyst and its synthetic method |
| CN110993797A (en) * | 2019-12-20 | 2020-04-10 | 储天新能源科技（长春）有限公司 | Non-lead double perovskite solar cell and preparation method thereof |
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| CN107805254A (en) * | 2017-09-18 | 2018-03-16 | 华南理工大学 | A kind of porphyrin small molecule perovskite cathode cushioning layer material and preparation method and application |
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| CN109939735A (en) * | 2017-12-20 | 2019-06-28 | 湖南科技大学 | A kind of phase transfer catalyst and its synthetic method |
| CN109939735B (en) * | 2017-12-20 | 2022-02-18 | 湖南科技大学 | Phase transfer catalyst and synthesis method thereof |
| CN108516978A (en) * | 2018-04-04 | 2018-09-11 | 华南理工大学 | A kind of asymmetrical porphyrin organic molecule cathode interface material and its preparation method and application |
| CN110993797A (en) * | 2019-12-20 | 2020-04-10 | 储天新能源科技（长春）有限公司 | Non-lead double perovskite solar cell and preparation method thereof |
| CN110993797B (en) * | 2019-12-20 | 2022-06-21 | 储天新能源科技（长春）有限公司 | Non-lead double perovskite solar cell and preparation method thereof |
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