CN102898430A - Preparation method and use of porphyrin micro/nano rods - Google Patents
Preparation method and use of porphyrin micro/nano rods Download PDFInfo
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Abstract
The invention discloses a method for preparing porphyrin micro/nano rods. The method comprises the following steps of: mixing a 0.1 to 0.3mmol/L ethanol solution of carboxylphenyl porphyrin with a hydrochloric acid with a pH of 1 to 3 uniformly; standing the mixed solution for 3 to 5; separating the product; and drying to obtain the product. The volume ratio of the ethanol solution of carboxylphenyl porphyrinethanol to the hydrochloric acid solution is 1:1 to 1:3. Self-assembled porphyrin micro/nano rods with a monocrystalline structure are prepared through simple operation without requiring harmful solvent. The method is suitable for mass production, the lengths of prepared porphyrin micro/nano rods are in a range from 40 to 60 micrometers, and some micro/nano rods may be hundreds of nanometers. When characterized by X-ray powder diffraction (XRD), the micro/nanorods may show distinct diffraction peaks in a small angle ranging from 5 to 100. The micro/nano rods are sensitive to light and can produce a light current which is nearly 10 times a dark current in a bias voltage area; and the light response of the micro/nano rods is very stable and repeatable, so the micro/nano rods can be used for manufacturing photoelectric devices.
Description
Technical field
The invention belongs to field of photovoltaic materials, relate to the preparation method of the micro-nano rod of a kind of porphyrin and the application in photoelectric device thereof.
Background technology
Along with the development trend of progress and the global integration of human society, traditional energy day by day reduce and environmental pollution becomes the subject matter of new millennium facing mankind.The exploitation of new green power is extremely urgent, is a good developing direction to the utilization of sun power.At present, the solar cell of commercialization mainly is to utilize inorganic HIGH-PURITY SILICON as the light trapping agent, but its expensive price makes prestige and steps back.Organic solar batteries is cheap, flexible because of it, be easy to the characteristics such as big area preparation forms another focus into people's research.Porphyrin Molecule since its unique conjugated structure and good photosensitivity, thermostability usually as photoelectric device and storage medium.On micro-nano-scale, many materials show the special performance that is different from body phase material.Development along with nanotechnology and nano science, how to make up the porphyrin photoelectric device of micro-nano-scale as novel photoelectric material and organic solar batteries, and improve its photoelectric transformation efficiency and become in recent years focus and the meaningful work of organic photoelectrical material area research.Many scientists have utilized the method (reprecipitation method, surfactant method etc.) of multiple self-assembly to prepare the porphyrin micro Nano material of different structure.Such as document " Three-Dimensional Self-organization of Supramolecular Self-Assembled Porphyrin Hollow Hexagonal Nanoprisms " Jin-Song Hu, J. AM. CHEM. SOC. 2005, v127, p17090-17095, disclose a kind of by four (4-pyridyl) zinc porphyrin (zinc meso-tetra (4-pyridyl) porphyrin, ZnTPyP) nanoprisms of self-assembly (nanoprisms), then this nanoprisms length is less than 1 μ m, and mainly be distributed between 520～540nm, this length causes the difficulty on using.
Summary of the invention
The object of the present invention is to provide the another kind of method for preparing the micro-nano rod of porphyrin, make the micro-nano excellent length of porphyrin of gained reach tens microns.
Another object of the present invention provides the application of the micro-nano rod of porphyrin that a kind of aforesaid method makes.
A kind of method for preparing the micro-nano rod of porphyrin, the method is: tetracarboxylic phenyl porphyrin ethanolic soln and the pH that with concentration is 0.1～0.3mmol/L is that 1～3 hydrochloric acid soln mixes, mix rear Static and put 3～5d, obtain product through separation, drying again, the volume ratio of described tetracarboxylic phenyl porphyrin ethanolic soln and hydrochloric acid soln is 1:1～1:3.
Further, described tetracarboxylic phenyl porphyrin obtains as follows: will be dissolved in the propionic acid solvent carboxyl benzaldehyde, and be heated to 125～130 ℃, and then drip pyrrole propanoic acid solution, drip rear continuation reaction 30～45min, the purified tetracarboxylic phenyl porphyrin that obtains of reaction product.
Further, be (1～1.1) to carboxyl benzaldehyde and pyrroles's mol ratio: 1.
Further, the method for reaction product purifying is: reaction product leaves standstill under 0～5 ℃ more first through concentrating under reduced pressure, separate out crude product, suction filtration, successively water, washing with alcohol, product after the washing is added to the water, regulates pH to 10～11, remove upper strata liquid, subnatant is used n-butanol extraction after transferring pH to 5～7 again, and the n-butanol layer anhydrous sodium sulfate drying that obtains filters, after filtrate decompression is concentrated, cross silicagel column, methanol-eluted fractions separates obtaining tetracarboxylic phenyl porphyrin.
The micro-nano rod of the porphyrin that aforesaid method makes is used for making photoelectric device.
Method of the present invention adopts amphipathic tetracarboxylic phenyl porphyrin, utilize intermolecular hydrogen bonding, π-π effect, by control pH value and ethanol water volume ratio, self-assembly goes out to have the micro-nano rod of porphyrin of single crystal structure, the method is simple to operate, need not the solvent that uses hazardness large, be applicable to prepare in a large number micro-nano rod, the micro-nano excellent length of prepared porphyrin mainly is distributed in the 40-60 micron, long reached at hundreds of micron, micro-nano excellent diameter is approximately 300-400nm, and profile cross-section is square, when characterizing with XRD, this micro-nano rod is at 5-10
0Little angular region show unique diffraction peak.The micro-nano rod of porphyrin that adopts the inventive method to make shows good photoelectric properties, and its electricity is led illumination responsive, and in bias region, photoelectric current is nearly ten times of dark current, and the photoresponse that its electricity is led has satisfactory stability and repeatability.
Description of drawings
Fig. 1 is the morphology characterization of the micro-nano rod of gained porphyrin of the present invention.
Fig. 2 is gained porphyrin ultraviolet-visible spectrum of the present invention and fluorescence spectrum.
Fig. 3 is the infrared spectrum of the micro-nano rod of gained porphyrin of the present invention.
Fig. 4 is the XRD spectra of the micro-nano rod of gained porphyrin of the present invention.
Fig. 5 is the capable performance characterization of photoelectricity of the micro-nano rod of gained porphyrin of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further details.
Structural formula:
The used porphyrin monomer of the present invention is the amphipathic tetracarboxylic phenyl porphyrin that has (namely 5,10,15,20-four (to carboxyl phenyl) porphyrin, TCPP), its structural formula as above, form the micro nano structure of one dimension in phase interface " from bottom to top " self-assembly by weak interactions such as its intermolecular hydrogen bonding and hydrophilic and hydrophobics, the volume ratio of pH value, ethanol and water by changing solution, the morphology change of control realization micro nano structure.
The preparation of tetracarboxylic phenyl porphyrin: in the 500mL there-necked flask, add 16.5g to carboxyl benzaldehyde (0.11mol) and 250mL propionic acid, oil bath is heated to little boiling (125～130 ℃) under the rapid stirring, then in 30min, drip 50mL and be dissolved with new steaming pyrroles (7mL, 0.1mol) propionic acid, continue reaction 30min.Change water distilling apparatus into after the cooling a little, after underpressure distillation concentrates out the 100mL propionic acid, stirring is cooled to room temperature, is put into the inner standing over night of refrigerator (0～5 ℃), and suction filtration gets crude product, crude product is used first twice of distilled water wash, use again absolute ethanol washing twice, get the puce solid, the puce solid is joined in the 50mL water, regulating pH with saturated sodium carbonate solution again is 10～11, this moment, the solution layering removed by filter upper strata liquid (oil phase), and subnatant (water) is regulated between pH to 5～7 with ammonium sulfate, add 3 * 50mL n-butanol extraction, static layering, the organic layer anhydrous sodium sulfate drying, filter concentrating under reduced pressure, separate after silica gel column chromatography, methyl alcohol is eluent, collects the first colour band (red-purple), is spin-dried for to get purple crystals 1.69g, be tetracarboxylic phenyl porphyrin, productive rate 8.6%.The sign of product 1: UV, visible light (UV-vis) spectrum, 421nm (Soret band), 514nm, 549nm, 589nm, 646nm (Q band); INFRARED SPECTRUM (KBr compressing tablet): v
(N-H)Pyrrole 3314cm
-1; d
(N-H)Pyrrole 965.8cm
-1(in planarity); 3427.7cm
-1(n
O-H), 1692.6cm
-1(n
C=O), 1606.5cm
-1(n
C=cPyhenl), 1402.3cm
-1(δ
O-H), 1275.4cm
-1(n
C-o), v
(C-H)2924cm
-1, 798.5cm
-1(to the characteristic absorbance of disubstituted benzenes), 1020.0cm
-1(stretching vibration of porphyrin ring skeleton);
1H NMR (d
6-DMSO) compose :-2.944 (s, 2H, NH), 8.326-8.384 (m, 16H, phenyl), 8.404-8.867 (m, 8H, β-pyrrole), 13.287 (s, 4H ,-COOH).
The preparation of micro-nano rod: above-mentioned freshly prepd tetracarboxylic phenyl porphyrin is added in the ethanol, being mixed with concentration is the tetracarboxylic phenyl porphyrin ethanolic soln (solution colour is pink) of 0.1～0.3mmol/L, then with the hydrochloric acid soln of pH=1～3, be that 1:1～1:3 mixes according to tetracarboxylic phenyl porphyrin ethanolic soln and hydrochloric acid soln volume ratio, stirring at room 5min, solution colour becomes light green, leave standstill 3～5d, cotton-shaped green precipitate appears, precipitation had both got product 2 through washing, filtration, vacuum-drying.Hydrochloric acid soln is by concentrated hydrochloric acid and water mixed preparing.
The morphology characterization of product 2 as shown in Figure 1, Figure 1A product that to be 0.1mmol/L tetracarboxylic phenyl porphyrin ethanolic soln mix by the 1:1 volume ratio with the hydrochloric acid of pH=1, can find out, gathering has occured in tetracarboxylic phenyl Porphyrin Molecule under the hydrochloric acid effect, forms singly to disperse the preferably club shaped structure of micro-or nano size.The terminal one-tenth of the micro-nano rod of part opening shape.Draw from statistics, the diameter of micro-nano rod is approximately 300～400 nm, and length mainly is distributed between the 40-60 micron, also can reach the hundreds of micron, if the pH of solution is further reduced, the micro-nano excellent length that then forms can reach grade.The SEM enlarged view can find out that this micro-nano excellent surface is accordion from Figure 1B, and has the formation of part defective, the sectional view of insertion to find out, this nanostructure is not circular configuration, but the rectangular parallelepiped of formation rule.Fig. 1 C is the details in a play not acted out on stage, but told through dialogues optical photograph of the micro-nano rod of this porphyrin, as can be seen from this figure, utilizes this simple method can prepare in a large number the micro-nano rod of porphyrin; Fig. 1 D is the transmission electron microscope picture of the micro-nano rod of single porphyrin, and insertion figure is electronics selected diffraction spectrum, can find out that from electron diffraction pattern the micro-nano rod of formation has single crystal structure.Therefore, above characterization data illustrates that we can prepare the micro-nano bar material of the porphyrin with single crystal structure in a large number by a kind of simple method.
On this basis, we further investigate the optical property of porphyrin nano rod.During the micro-nano rod of preparation porphyrin, the porphyrin the color of the solution becomes light green by pink, this is because Porphyrin Molecule after generation under the effect of acid is protonated, the porphyrin aggregate occurred, also can be found out by ultraviolet-visible spectrum (Fig. 2) Change of absorption of Porphyrin Molecule, when Porphyrin Molecule is not assembled, its 418nm(Soret with) strong absorption peak, 519,556 appear, 593,650nm(Q absorption band) locates to occur weak absorption peak (curve 1-solid line); After porphyrin ethanolic soln and mixed in hydrochloric acid, the absorption intensity at the 418nm place reduces, and approximately new absorption peak (curve 2-dotted line) appears in the 438nm place, and the 650nm Q of place band absorbs and strengthens simultaneously.Red shift occurs from the Soret band of Porphyrin Molecule, illustrate that Porphyrin Molecule has formed the J-aggregate in mixing solutions, this is because under the hydrochloric acid effect, nitrogen on the porphyrin ring occurs protonated, the coplanarity of porphyrin ring and peripheral hydroxy-acid group is increased, formed the J-state of aggregation of porphyrin by Intermolecularπ πinteraction.Because absorption peak red shift degree is little, illustrates that the aggregation extent of Porphyrin Molecule is not high, possible reason is that hydroxy-acid group easily and between solvent molecule or Porphyrin Molecule exists hydrogen bond, thereby the dimer of formation porphyrin is corresponding to new absorption peak occurs at the 438nm place.Also can find out from the fluorescence Spectra (curve 3 of 600-800nm and curve 4 among Fig. 2) of Fig. 2 mesoporphyrin molecule, Porphyrin Molecule fluorescence appears at about 650nm and 720nm, correspond respectively to Soret and the Q band emission peak (curve 3-solid line) of Porphyrin Molecule, after forming Porphyrin dimer, its fluorescence peak generation red shift and broadening, fluorescence peak appear at (curve 4-dotted line) about 650nm.
Fig. 3 is the infared spectrum of the micro-nano rod of porphyrin (curve 2) and porphyrin powder (curve 1).From whole spectrogram, the two does not have obvious difference.After the Porphyrin Molecule acidifying forms dimer, to compare with the vibration of Porphyrin Molecule, main difference concentrates on 1100-1500cm
-1Place, this zone mainly are the flexible and flexural vibration of pyrrole ring, and the porphyrin micro nano structure of formation is at this domain oscillation strength reduction; 1350cm in the Porphyrin Molecule
-1The place is the stretching vibration of C-N, and almost disappears in the micro-nano bar structure that forms; 1225 cm in the Porphyrin Molecule
-1The place does not almost have vibration peak, and strong vibration signal occurs in the aggregate that forms.In addition from the high band district, 3314cm in the micro-nano rod of porphyrin
-1The stretching vibration of the N-H of place disappears, and the dimeric structure that has porphyrin in the porphyrin micro nano structure that forms is described.Therefore by the sign explanation of INFRARED SPECTRUM, the micro-nano rod of our resulting porphyrins may be to form the dimer gathering by the porphyrin acidifying to form, and forms mechanism in order better to understand it, and we carry out the sign of XRD to it.Can find out from the XRD of the micro-nano rod of Fig. 4 porphyrin (curve 2) and porphyrin compound powder (curve 1), after forming the porphyrin aggregate, some new diffraction peaks occur, have certain molecular ordered arrangement in this explanation porphyrin aggregate.Can find out that from XRD the micro-nano rod of porphyrin formation is at 5-10
0Diffraction peak is arranged in the scope, illustrate in this micro nano structure to have laminate structure.Therefore, composing us by INFRARED SPECTRUM and XRD can draw: the micro-nano rod of formation may be by protonated Porphyrin Molecule (H
2TCPP2
+) π-π effect, peripheral carboxylic acid (COOH) group and another molecule H
2TCPP
2+Form the coefficient result of hydrogen bond, thereby form the one-dimentional structure of porphyrin aggregate.
Photoelectric properties characterize:
The micro-nano rod of porphyrin that the present invention makes is transferred to SiO by the solution evaporation method
2(300nm)/the Si substrate on, prepare electrode by mask plate after dry, mask plate and micro-nano excellent perpendicular direction, after fixing mask plate with adhesive tape, then at the golden film about vacuum evaporation 30nm on the substrate, after evaporation is complete, remove mask plate, just obtained the nano photoelectric device of a upper contact, the interval 10 μ m(between the electrode are shown in the insertion figure of Fig. 5 A).
Two probe method is adopted in the test of nano photoelectric device, the atmosphere at room temperature environment, and test macro is equipped with monochromatic source.Fig. 5 A has provided under details in a play not acted out on stage, but told through dialogues (dark curve) and 5mW light Continuous irradiation (light curve), the I-V curve of prepared nano photoelectric device.What can obviously find out is that the electricity of nano-device is led illumination very responsive.In whole bias region, photoelectric current all has nearly ten times growth than dark current.Fig. 5 B has provided the light activated switching response curve of nano photoelectric device paired pulses incident (device bias is 30V).Under rayed, the photoelectric current of nano-device is very large; When closing light source, electric current drops to minimum in 40S, opens light source again, and electric current has been raised to again maximum in 120S.Through repeatedly " opening (on) ", the circulation of " closing (off) " light source, the photoresponse that electricity is led does not still reduce.Therefore, the electric leaded light response of the micro-nano rod of porphyrin shows satisfactory stability and repeatability.
Claims (6)
1. method for preparing the micro-nano rod of porphyrin, it is characterized in that: tetracarboxylic phenyl porphyrin ethanolic soln and the pH that with concentration is 0.1～0.3mmol/L is that 1～3 hydrochloric acid soln mixes, mix rear Static and put 3～5d, obtain product through separation, drying again, the volume ratio of described tetracarboxylic phenyl porphyrin ethanolic soln and hydrochloric acid soln is 1:1～1:3.
2. the described method for preparing the micro-nano rod of porphyrin according to claim 1, it is characterized in that, described tetracarboxylic phenyl porphyrin is to obtain as follows: will be dissolved in the propionic acid solvent carboxyl benzaldehyde, be heated to 125～130 ℃, then drip pyrrole propanoic acid solution, drip rear continuation reaction 30～45min, the purified tetracarboxylic phenyl porphyrin that obtains of reaction product.
3. the described method for preparing the micro-nano rod of porphyrin according to claim 2, it is characterized in that: the mol ratio to carboxyl benzaldehyde and pyrroles is (1～1.1): 1.
4. the described method for preparing the micro-nano rod of porphyrin according to claim 2, it is characterized in that, the method of reaction product purifying is: reaction product is first through concentrating under reduced pressure, under 0～5 ℃, leave standstill again, separate out crude product, suction filtration, successively water, washing with alcohol, product after the washing is added to the water, regulate pH to 10～11, remove upper strata liquid, subnatant is used n-butanol extraction after transferring pH to 5～7 again, the n-butanol layer anhydrous sodium sulfate drying that obtains, filter, after filtrate decompression is concentrated, cross silicagel column, methanol-eluted fractions separates obtaining tetracarboxylic phenyl porphyrin.
5. micro-nano rod of porphyrin for preparing by the arbitrary described method of claim 1～4.
6. the application of the micro-nano rod of the described porphyrin of claim 5 is characterized in that, is used for making photoelectric device.
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Cited By (2)
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| CN103849376A (en) * | 2014-03-20 | 2014-06-11 | 陇南师范高等专科学校 | Method of preparing porphyrin nanogold composite material with core-shell structure |
| CN107176958A (en) * | 2017-06-01 | 2017-09-19 | 熊子达 | 5,10,15,20 4 (4 carboxyl phenyl) porphyrins with nanostructured and preparation method thereof |
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Cited By (2)
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| CN103849376A (en) * | 2014-03-20 | 2014-06-11 | 陇南师范高等专科学校 | Method of preparing porphyrin nanogold composite material with core-shell structure |
| CN107176958A (en) * | 2017-06-01 | 2017-09-19 | 熊子达 | 5,10,15,20 4 (4 carboxyl phenyl) porphyrins with nanostructured and preparation method thereof |
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