CN106946893A - A kind of binary channels crown ether porphyrin fullerene array and its production and use - Google Patents

A kind of binary channels crown ether porphyrin fullerene array and its production and use Download PDF

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CN106946893A
CN106946893A CN201710212345.7A CN201710212345A CN106946893A CN 106946893 A CN106946893 A CN 106946893A CN 201710212345 A CN201710212345 A CN 201710212345A CN 106946893 A CN106946893 A CN 106946893A
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porphyrin
crown ether
fullerene
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宋非非
马盼
阚玲玲
王瑜成
朱沛华
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University of Jinan
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Abstract

The invention belongs to material chemistry technical field, and in particular to a kind of binary channels crown ether porphyrin fullerene（D‑A）Array and its production and use.The present invention utilizes three hydrogen on the amine after being protonated on fullerene and [N H ... the O] hydrogen bond at three oxygen formation, three centers on crown ether, the fulleropyrrolidine derivative in connection on the ITO substrates with crown ether porphyrin vertical stratification, so as to obtain orderly electronics to by (D A) supramolecular system.It is bonded and is connect by Si O between crown ether porphyrin and electrode in the binary channels crown ether porphyrin fullerene array of the present invention, is bonded and connect by Si O Si between crown ether porphyrin；It is connected between (four butylamine) 3,4 fullerene chemistries of 2 phenyl 5 and 5,10,15,20 4 (hat of benzo 15 5) porphyrins by the complexing of ammonium root cation crown ether；Therefore, its Stability Analysis of Structures.In addition, the binary channels crown ether porphyrin fullerene array of the present invention can also significantly improve the photoelectricity flow of electrode；In the case of fixed voltage 0.3V, the incrementss of photoelectric current are 1.67 x 10‑6 A。

Description

A kind of binary channels crown ether porphyrin-fullerene array and its production and use
Technical field
The invention belongs to material chemistry technical field, and in particular to a kind of binary channels crown ether porphyrin-fullerene（D-A）Array And its production and use.
Background technology
D-A (D-A) hetero-junctions is a kind of core texture of current techniques, in transistor, light emitting diode, photovoltaic There is extraordinary potential using value, because its controllable Charge Dynamics in terms of device.Twin-channel electronics to- Substantial amounts of hetero-junctions can be provided by (D-A) array, this is conducive to the quick fortune for producing effective separation of charge and separation electric charge It is defeated.Because the swift electron transfer reaction of porphyrin-fullerene compound has very small Reorganization Energy, porphyrin-fullerene is combined System has proven to be a kind of preferable D-A arrays construction matrix.At present, there are the Many researchers can be by molecule Self-assembling method obtains the porphyrin-fullerene nanostructured of non-covalent interaction connection.Because electric charge is from porphyrin-fullerene The transfer rate of compound to electrode is fast, then twin-channel electronics to-should by vertical arrangement of (D-A) array on electrode It is perfect condition.Therefore, the binary channels D-A arrays that vertical arrangement is obtained on electrode are still one that current researcher faces Big challenge.
The content of the invention
The present invention provides a kind of binary channels crown ether porphyrin-fullerene（D-A）Array and preparation method thereof and purposes.
A kind of binary channels crown ether porphyrin-fullerene array, its structure such as formulaIt is shown：
；
Wherein, formulaIn " A " structure such as formulaIt is shown：
；
FormulaIn " B " be fullerene；
FormulaIn be bonded and connect by " Si-O " between " A " and " O ".Above-mentioned binary channels crown ether porphyrin-fullerene array, in multilayer knot Structure, is bonded by " Si-O-Si " connects between layers.
Above-mentioned binary channels crown ether porphyrin-fullerene array, in Nanoparticulate, particle high 31-35 nm, wide 120-280 nm。
Above-mentioned binary channels crown ether porphyrin-fullerene array, is with 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins and 2- Phenyl -5- (four butylamine) -3,4- fullerene chemistries are prepared from for primary raw material.
The present invention utilizes three hydrogen on the amine after being protonated on fullerene and three oxygen formation, three centers on crown ether [N-H ... O] hydrogen bond, the fulleropyrrolidine derivative in connection on the ITO substrates with crown ether porphyrin vertical stratification, so as to obtain Orderly electronics to-by (D-A) supramolecular system.Crown ether porphin in the binary channels crown ether porphyrin-fullerene array of the present invention It is bonded and is connect by Si-O between quinoline and electrode, is bonded and connect by Si-O-Si between crown ether porphyrin；2- phenyl -5- (four butylamine) -3, Pass through the complexing of ammonium root cation-crown ether between 4- fullerene chemistries and 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrin Effect connection；Therefore, its Stability Analysis of Structures.In addition, the binary channels crown ether porphyrin-fullerene array of the present invention can also significantly improve electricity The photoelectricity flow of pole；In the case of fixed voltage -0.3V, the incrementss of photoelectric current are 1.67 x 10-6 A。
A kind of preparation method of above-mentioned binary channels crown ether porphyrin-fullerene array, comprises the following steps：
（1）Prepare one-dimensional crown ether porphyrin array of (Benzo15crown5 derivatives) porphyrins of 5,10,15,20- tetra- perpendicular to electrode surface；
（2）The electrode that there is one-dimensional crown ether porphyrin array on surface is put into 2- phenyl -5- (four butylamine) -3,4- fullerene chemistries molten Soak after 1-8 h and take out in liquid, be cleaned by ultrasonic, dry, you can.
Above-mentioned preparation method, step 1 can be realized using existing method, it would however also be possible to employ following step is realized：
5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins are dissolved in anhydrous solvent, silicon tetrachloride is then added, is then placed in Electrode soaks number 1-7 h, electrode is taken out, ultrasonic 1 min in chloroform soln（The effect of ultrasound removes physics on electrode The crown ether porphyrin of absorption）, electrode is taken out, dried, that is, obtains the one-dimensional crown ether porphyrin array perpendicular to electrode surface；
The electrode surface hydroxy functional groups, such as ITO conductive electrodes or FTO conductive electrodes.
Prepared one-dimensional crown ether porphyrin array is in nano whiskers；It is bonded and is connect by O-Si between electrode and crown ether porphyrin, It is bonded and is connect by Si-O-Si between crown ether porphyrin.
Above-mentioned preparation method, in the preparation process of one-dimensional crown ether porphyrin array, with the increase of soak time, one-dimensional hat The increase of ether porphyrin array nano whiskers quantity；But, soak time is too short can cause acicular texture occur without or content seldom, Photoelectric properties are very poor；And occur obvious compound clustering phenomena in long soaking time, solution, non-bright solution state, The compound of self aggregation very indissoluble solution, it is impossible to proceed to steep piece；Therefore, the present invention limits the soak time of step 1 as 1-7 h.When soak time is 5 h, needle-like average height progressively increases to 35 nm；Highly reach after 35 nm, with soak time Increase, will not highly increase, photoelectric properties do not have significant change.It is therefore preferable that step 1 soak time be 5 h.
In above-mentioned preparation method, step 1,5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins are dissolved in anhydrous solvent and formed Concentration is 0.1-1 mmol/L crown ether porphyrin solution, 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins and silicon tetrachloride Mol ratio is 1: 5-30.
In above-mentioned preparation method, step 2, soak time is too short（Less than 1 h）, 2- phenyl -5- (four butylamine) -3,4- fullerene pyrroles Coughing up alkane can not fully be combined with one-dimensional crown ether porphyrin array, cause photoelectric properties poor；And long soaking time（Higher than 8 h）, one Dimension crown ether porphyrin array can be destroyed, and cause photoelectric properties poor；Therefore, the present invention limits soak time as 1-8 h.And soak 7 The photoelectric properties for the binary channels crown ether porphyrin-fullerene array that h is obtained are more preferable, it is preferred, therefore, that the soak time of step 2 is 7 h.
Above-mentioned preparation method, because one-dimensional crown ether porphyrin array is combined with chemical covalent bonds, material is stable, will not be because of Solvent is different and dissolves；So, in step 2, the solvent of 2- phenyl -5- (four butylamine) -3,4- fullerene chemistry solution is only Meet the requirement of " dissolving 2- phenyl -5- (four butylamine) -3,4- fullerene chemistries "；Such as methanol.
In above-mentioned preparation method, step 2,2- phenyl -5- (four butylamine) -3,4- fullerene chemistries solution is molten using saturation Liquid energy ensures that fullerene can be acted on sufficiently with crown ether porphyrin；So, 2- phenyl -5- (four butylamine) -3,4- fullerene pyrroles Alkane solution is preferably saturated solution.
A kind of purposes of above-mentioned binary channels crown ether porphyrin-fullerene array, for photoelectric properties detection.
The present invention is the property being complexed using fullerene ammonium root cation easily with crown ether on porphyrin, with crown ether porphin Upper fulleropyrrolidine derivative is connected on the ITO substrates of quinoline vertical stratification, thus obtain orderly electronics to-it is super by (D-A) Molecular system.The D-A systems of preparation are used for photoelectric device, found compared to crown ether porphyrin, the system photoelectric current substantially increases. Crown ether porphyrin-fullerene nano composite material preparation process of the present invention is simple, can largely prepare at room temperature, it is in light There is potential application value in terms of electrical part.
Compared with prior art, the invention has the advantages that：
（1）Binary channels crown ether porphyrin-fullerene of the present invention（D-A）The preparation method of array is simple solution infusion method, without Complex device, it is simple and easy to apply；
（2）The preparation method that the present invention is used can be carried out at room temperature, be easy to batch production；
（3）Binary channels crown ether porphyrin-fullerene array prepared by the present invention, 2- phenyl -5- (four butylamine) -3,4- fowlers therein Connected between alkene pyrrolidines and 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins by crown ether-cation complex effect, can Well with the porphyrin crown ether moiety generation complexing being vertically arranged in ITO electrode, so as to form the nanometer of high-sequential Structure, the array of acquisition is more stable.
（4）Binary channels crown ether porphyrin-fullerene of the present invention（D-A）Array photoelectric excellent performance, is in particular in -0.3V Under voltage, the incrementss of the array photoelectric stream are up to 1.67 x 10-6 A/cm2；It is expected in solar cell, organic electro-optic device etc. There is important application in field.
In the present invention, described 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins, its molecular formula is C76H90N4O20, it is tied Structure formula is：
；Its preparation method refers to document：Inorg. Chem. 2004, 43, 6969-6978；
2- phenyl -5- (four butylamine) -3, the 4- fullerene chemistries, its molecular formula is C72H18N2 +, its structural formula is：
；Its preparation method refers to document：Chem. Eur. J. 2005, 11, 4416 - 4428.
The fullerene, its molecular formula is C60, its structural formula is：。
Brief description of the drawings
Fig. 1 soaks 1 for the ITO conductive electrodes of embodiment 1 in 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrin solution h（A, D）、 3 h（B, E）、5 h（C, F）2D and 3D AFM scheme；
Fig. 2 is ITO conductive electrode of the embodiment 2 containing 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrin orthogonal array in richness Strangle 2D and 3D the AFM figures that 7 h are soaked in alkene pyrrolidines saturated solution；
The one-dimensional crown ether porphyrin array for the vertical arrangement that Fig. 3 embodiments 1 or 2 are obtained（Dark-grey colo(u)r streak）With binary channels crown ether porphyrin- Fullerene（D-A）Array（Black line）Photocurrent-time curve；
The binary channels crown ether porphyrin-fullerene that Fig. 4 embodiments 2 are obtained（D-A）Array stability test curve.
Embodiment
The specific embodiment of the invention is further described below.
The one-dimensional crown ether porphyrin array preparation method that embodiment 1 is arranged vertically
ITO conductive electrodes are used into toluene, acetone, ethanol, deionized water successively（Reagent used herein is not right, it should be acetone, NaOH（1 mol/L）Second alcohol and water（Volume ratio 1:1）Mixed solution, deionized water）It is cleaned by ultrasonic 10-30 min respectively, Then dry；Obtain the electrode that hydroxy functional group is contained on surface.Weigh 2.1 mg 5,10,15,20- tetra- (Benzo15crown5 derivatives) porphins Quinoline is dissolved in 15 mL chloroforms, is then filtered, in assembling bottle in obtain 0.1 mmol/L 5,10,15,20- tetra- (benzo- 15- crown-s 5) porphyrin chloroform soln.2 μ L silicon tetrachlorides are taken to be added to 5,10,15,20- tetra- (Benzo15crown5 derivatives) In the chloroform soln of porphyrin, the electrode that hydroxy functional group is contained on surface is put into, soaks electricity is taken out after 1 h, 3 h, 5 h respectively Pole, electrode is put into a small beaker containing anhydrous chloroform and dried under ultrasound 1min, nitrogen stream（Also can be in sky Dried in gas）, obtain being vertically arranged in the one-dimensional crown ether porphyrin array of ITO conductive electrodes.
The binary channels crown ether porphyrin-fullerene of embodiment 2（D-A）Array
Using methanol as solvent, saturated solution is made in 2- phenyl -5- (four butylamine) -3,4- fullerene chemistries, then will be implemented The vertical row obtained after 5 h is soaked in example 1 show the ITO conductive electrodes of one-dimensional crown ether porphyrin nano structure and be placed in one immersion 7 H, takes out conductive electrode, and electrode is put into a small beaker containing anhydrous chloroform and carried out in ultrasonic 1 min, nitrogen stream Dry（Also it can dry in atmosphere）, obtain being vertically arranged in the binary channels crown ether porphyrin-fullerene of ITO conductive electrodes（D-A） Array.
The binary channels crown ether porphyrin-fullerene of embodiment 3（D-A）Array photoelectric performance detection
Photoelectric properties test device is built by laboratory, and test process is in a comparatively gentle environment（Room temperature, the external world Under atmospheric pressure and dry air）Lower progress.Electrolyte is Na2SO4Concentration is molten for 0.1 mol/L PBS (pH 7.4) bufferings Liquid, tester is CHI760C electrochemical workstations, uses traditional three-electrode system（ITO conductive electrodes containing material are Working electrode, Ag/AgCl electrodes are reference electrode, and platinum plate electrode is to electrode）, light source is CEL-S500/350 xenon sources, Simulate 100 mW cm-2Sunshine, test be photoelectric current and time under -0.3 V relation.Test result：Embodiment 2 is made Standby binary channels crown ether porphyrin-fullerene（D-A）Array presents excellent electric conductivity, and its photoelectric current under -0.3 V is close Spend for 1.67 x 10-6 A/cm2, and the density of photocurrent of the one-dimensional crown ether porphyrin array being arranged vertically under the same conditions is only It is 6.96 x 10-7 A/cm2。
In addition, the present invention has also carried out following experiment：
The ITO conductions that the vertical row obtained after 1 h, 3 h, 7 h shows one-dimensional crown ether porphyrin nano structure are soaked using embodiment 1 Electrode, using the preparation condition of embodiment 2, can obtain the binary channels crown ether porphyrin-fowler for being vertically arranged in ITO conductive electrodes Alkene（D-A）Array.
Embodiment 1 is soaked to the vertical row obtained after 5 h show the ITO conductive electrodes of one-dimensional crown ether porphyrin nano structure and put In 2- phenyl -5- (four butylamine) -3,4- fullerene chemistry saturated solutions same as Example 2, respectively by soak time 1 h, 2 h, 3 h, 4 h, 6 h, 7 h, 8 h are adjusted to, other conditions be the same as Example 2 can obtain and be vertically arranged in ITO conductions The binary channels crown ether porphyrin-fullerene of electrode（D-A）Array.

Claims (9)

1. a kind of binary channels crown ether porphyrin-fullerene array, its structure is as shown in formula：
；
Wherein, formulaIn " A " structure such as formulaIt is shown：
；
FormulaIn " B " be fullerene；
FormulaIn be bonded and connect by " Si-O " between " A " and " O ".
2. binary channels crown ether porphyrin-fullerene array according to claim 1, it is characterised in that in Nanoparticulate, Grain high 31-35 nm, wide 120-280 nm.
3. binary channels crown ether porphyrin-fullerene array according to claim 1 or claim 2, it is characterised in that be with 5,10,15, (Benzo15crown5 derivatives) porphyrins of 20- tetra- and 2- phenyl -5- (four butylamine) -3,4- fullerene chemistries are prepared from for primary raw material 's.
4. a kind of preparation method of binary channels crown ether porphyrin-fullerene array described in claim 1,2 or 3, it is characterised in that bag Include following steps：
Prepare one-dimensional crown ether porphyrin array of (Benzo15crown5 derivatives) porphyrins of 5,10,15,20- tetra- perpendicular to electrode surface；
The electrode that there is one-dimensional crown ether porphyrin array on surface is put into 2- phenyl -5- (four butylamine) -3,4- fullerene chemistry solution Taken out after middle immersion 1-8 h, be cleaned by ultrasonic, dry, you can.
5. preparation method according to claim 4, it is characterised in that step 1 is realized using following step：
5,10,15,20- tetra- (Benzo15crown5 derivatives) porphyrins are dissolved in anhydrous solvent, silicon tetrachloride is then added, is then placed in Electrode soaks number 1-7 h, electrode is taken out, ultrasonic 1 min in chloroform soln, and electrode is taken out, dried, that is, is hung down Directly in the one-dimensional crown ether porphyrin array of electrode surface；
The electrode surface hydroxy functional groups, such as ITO conductive electrodes or FTO conductive electrodes.
6. the preparation method according to claim 4 or 5, it is characterised in that the soak time of step 1 is 5 h.
7. preparation method according to claim 6, it is characterised in that in step 1,5,10,15,20- tetra- (phendioxin 5- crown-s 5) porphyrin is dissolved in the crown ether porphyrin solution that anhydrous solvent formation concentration is 0.1-1 mmol/L, 5,10,15,20- tetra- (phendioxin 5- Crown- 5) mol ratio of porphyrin and silicon tetrachloride is 1: 5-30.
8. preparation method according to claim 7, it is characterised in that the soak time of step 2 is 2- benzene in 7 h, step 2 Base -5- (four butylamine) -3,4- fullerene chemistries solution is saturated solution.
9. the purposes of binary channels crown ether porphyrin-fullerene array described in a kind of claim 1,2 or 3, for photoelectric properties detection.
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