CN103102353A - Free porphyrin, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses free porphyrins, and a preparation method and application thereof. A method of modifying simple porphyrin is employed to synthesize three free porphyrins (3a, 3b, 3c), where 3b and 3c are new porphyrins; means of elemental analysis, infrared spectrum, UV-vis spectra and 1H NMR are adopted to characterize the prepared porphyrin compounds containing tailed imidazole. According to a test on catalytic performance of free porphyrins (3a-3b) on a Li / SOCl2 battery, the results show that compared with a bare battery, the above porphyrin compounds prolong discharge time of the Li / SOCl2 battery to different degrees, when the battery discharges to 2V, under conditions of room temperature of 25 DEG and resistance of 40 ohm; and capacity of the battery is increased substantially. Therefore, free porphyrins can affect electron transfer in the electronic Li / SOCl2 battery, so as to affect performance of the battery.
Description
Technical field
The invention belongs to technical field of chemistry, relate to a kind of free porphyrin and its production and use.
Background technology
Lithium/thinly chloride battery is a kind of up-and-coming novel high-energy chemical power source.The open circuit voltage of this battery can reach 3.65V, and operating voltage, in the 3.3V left and right, is generally the highest in lithium cell.This battery also possesses as large as energy density (150w.h/kg) simultaneously, storage time long (~ 10years), operating temperature range wide (55 ~ 85 ℃), the plurality of advantages such as discharge time is long.Lithium/thinly chloride battery is the current the highest a kind of battery of specific energy in the battery of practical application in the world, therefore obtained research widely at aspects such as petroleum prospecting, marine ship heavy industry, military project, medical treatment and applied.Make actual output specific energy but the comparatively distinct issues that such battery exists in discharge process are polarization of electrode, much smaller than theory output specific energy, seriously restricted the use of such battery.
In order to solve lithium/thinly chloride battery system drawback in actual applications, improve battery performance, many scholars have carried out certain research work.Mainly comprise the research of screening and the improvement, particularly anode catalyst of positive electrode material.At present, Macrocyclic polyamine class title complex as: ten four-wheel alkene title complexs, phthalocyanine and Schiff bases title complex etc. are the main study subjects of lithium/thinly chloride battery catalyzer, and porphyrins and phthalocyanine-like compound all have the structure of high conjugation, good thermostability, the good premium propertiess such as electronic conduction, and in thionyl chloride electrolytic solution, impact due to solution polarity, the solvability of porphyrin is higher than phthalocyanine, be conducive to like this go in catalyzed reaction that more porphyrin participates in battery, be conducive to the transfer of electronics in cell reaction.Therefore, porphyrin compound is applied to Li/SOCl
2the research of battery system, improve the battery performances such as its sparking voltage, cell container with expectation, have important researching value and good development prospect.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of free porphyrin and its production and use, the synthetic reaction condition gentleness, productive rate is higher, be easy to the simple porphyrin of preparation, then its periphery carried out the modification of structure, thereby obtain final target Porphyrin Molecule.The method that employing is modified simple porphyrin, synthesized three free porphyrins (3a, 3b, 3c) that contain imidazolyl, and be applied in lithium thionyl chloride cell, studied its impact on battery performance.
Its technical scheme is as follows:
A kind of free porphyrin, its structural formula is:
A kind of preparation method of free porphyrin comprises the following steps:
The first step, 5-(4-hydroxy phenyl)-10, 15, synthesizing of 20-Triphenylporphyrin (1a), adopt ripe Alder propionic acid method, concrete operation step is: add about 150mL propionic acid in the 500mL three-necked bottle, then phenyl aldehyde 4.60mL (45mmol) and p-Hydroxybenzaldehyde 1.83g (15mmol) are dissolved in respectively in the 10mL propionic acid, be added in three-necked bottle, heating magnetic agitation are fully mixed the two, oil bath is heated to propionic acid and refluxes, slowly in reactor, add 10mL to be dissolved with the propionic acid solution that 4.16mL (60mmoL) newly steams the pyrroles, after dropwising, continue back flow reaction approximately 1 hour, stopped reaction, standing cooling, reduction vaporization, remove the propionic acid solvent, evaporate to dryness as far as possible, add about 100mL ethanol in reactor, be put in standing over night in refrigerator, decompress filter, and colourless to filtrate with ice washing with alcohol suction filtration product, obtain the purple solid, the crude product obtained is dissolved with methylene dichloride, chromatographic silica gel is stationary phase, methylene dichloride is eluent, carry out column chromatography for separation, collect the second chromatographic band, obtain target product 1a,
Second step, three kinds contain the synthetic of bromine alkoxyporphyrin (2a, 2b, 2c): with 5-(4-(2-bromine oxethyl) phenyl)-10,15,20-Triphenylporphyrin (2a) synthesize example, concrete operations are: the anhydrous DMF that adds about 10ml heavily to steam in the three-necked bottle of 50ml, then by glycol dibromide (0.80ml, 9.6mmol) add wherein, claim anhydrous K
2cO
3(0.40g, 2.89mmol) add wherein, be heated to 80 ℃, compound 1a (0.20g, 0.32mmol) be dissolved in the DMF solution of about 5ml, slowly drop in reaction vessel, pass into N2, maintain temperature of reaction at 80 ℃, TLC monitoring reaction process to reaction approaches fully, react approximately 6 hours, stopped reaction, underpressure distillation remove DMF and unreacted complete 1, the 2-ethylene dibromide, obtain thick product, thick product is dissolved in a small amount of trichloromethane, trichloromethane/normal hexane (V/V=5:1) mixed solvent of take is eluent, chromatographic silica gel is that stationary phase carries out the column chromatography for separation purification, collect the first chromatographic band and obtain target product (2a), compound 5-(4-(3-bromine propoxy-) phenyl)-10, 15, 20-Triphenylporphyrin (2b) and 5-(4-(4-bromine butoxy) phenyl)-10, 15, synthesizing of 20-Triphenylporphyrin (2c) is similar to the preparation process of compound (2a), just by reaction raw materials 1, the 2-ethylene dibromide changes respectively 1 into, 3-dibromopropane and 1, the 4-dibromobutane,
The 3rd step, three kinds contain the synthetic of imidazolyl porphyrin (3a, 3b, 3c): 5-[4-(2-imidazolyl)-oxyethyl group] phenyl-10,15, the synthetic concrete steps of 20-Triphenylporphyrin (3a) are: in single neck bottle of 50mL, add about 15mL heavily to steam DMF as solvent, by compound 2a (0.10g, 0.13mmol) and imidazoles (0.9g, 13mmol) add wherein, then add anhydrous K
2cO
3(0.50g, 3.6mmol), under room temperature, lucifuge stirs, the process of TLC monitoring reaction is to reacting completely, react 20 hours, DMF is removed in underpressure distillation, then the mixture of reaction is dissolved in the trichloromethane of 20mL, be washed till neutrality with the distilled water of 20mL, after extraction, the decompression rotary evaporation, concentrate to obtain thick product, then take chromatographic silica gel as stationary phase, trichloromethane/ethanol (V/V=20:1) carries out column chromatographic isolation and purification for eluent, collect the first chromatographic band and obtain target product (3a), compound 5-[4-(3-imidazolyl)-propoxy-] phenyl-10, 15, 20-Triphenylporphyrin (3b) and 5-[4-(4-imidazolyl)-butoxy] phenyl-10, 15, synthetic and the 3a's of 20-Triphenylporphyrin (3c) is synthetic similar, just change respectively reaction raw materials compound 2a into compound 2b and 2c.
Free porphyrin of the present invention is at preparation Li/SOCl
2application in battery.
Beneficial effect of the present invention:
Free porphyrin compound of the present invention is to Li/SOCl
2battery has catalytic performance preferably, can significantly improve its battery performance.
The accompanying drawing explanation
Fig. 1 is the synthetic route chart of the free imidazoles porphyrin of the present invention;
Fig. 2 is the infrared spectrum of imidazoles porphyrin 3a;
Fig. 3 is the infrared spectrum of imidazoles porphyrin 3b;
Fig. 4 is the infrared spectrum of imidazoles porphyrin 3c;
Fig. 5 is the ultraviolet-visible light spectrogram of imidazoles porphyrin 3a;
Fig. 6 is the ultraviolet-visible light spectrogram of imidazoles porphyrin 3b;
Fig. 7 is the ultraviolet-visible light spectrogram of imidazoles porphyrin 3c;
Fig. 8 is the nmr spectrum of imidazoles porphyrin 3a;
Fig. 9 is the nmr spectrum of imidazoles porphyrin 3b;
Figure 10 is the nmr spectrum of imidazoles porphyrin 3c;
Figure 11 is the Li/SOCl of porphyrin catalysis
2the battery discharge curve;
Figure 12 is the Li/SOCl of porphyrin catalysis
2average voltage;
Figure 13 is the Li/SOCl of porphyrin catalysis
2relative energy capacity of battery.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described in more detail.
The preparation method's of free porphyrin route map as shown in Figure 1.
Synthetic porphyrin and the structural characterization of intermediate product
With C, H, the N constituent content in elemental analyser (Vario EL-III) (Germany) test title complex, with ultraviolet-visual spectrometer (UV1800, shimadzu) uv-vis spectra of (Daojin International Trade (Shanghai) Co., Ltd.) test porphyrin, use WRS-1
anumeral melting point instrument (Shanghai Physics Optics Instrument Factory) is tested its fusing point, with infrared spectrometer (BEQ UZNDX550-FTIR, KBr compressing tablet) Bruker, and the infrared spectra of (Germany) test title complex.Carry out the nuclear-magnetism sign by NMR spectrometer with superconducting magnet (VARIAN INOVA400MHz, Varian, theU.S).
Porphyrin is for the lithium/thinly chloride battery performance test
The simulated battery that the tetrafluoroethylene of take is material, negative pole adopts the metal lithium sheet that light is clean, and carbon film is anodal, and polypropylene screen (PP film) is barrier film.Before assembled battery, anodal carbon film, barrier film, catalyzer, battery container be at 70 ℃ of vacuum-drying 4h, then in relative humidity, is less than assemble in 1% dry air atmosphere, by porphyrin compound (2 * 10
-3molL
-1) be dissolved in electrolytic solution, be injected in battery mould and carry out experiment test.The battery testing condition is: in the atmosphere of dry air, the temperature that controls environment 23-25 ℃, by the battery that assembles at external constant resistance R
eduring=40 Ω, continuous discharge, to 2V, is recorded a secondary data every 30s, obtains battery discharge voltage relation over time.
The fusing point of porphyrin, infrared spectra, uv-vis spectra and nuclear-magnetism characterize
Synthetic porphyrin is done to series and characterize, characterization data is in Table 1.From data, can find out, synthetic porphyrin results of elemental analyses and theoretical value approach, the infrared spectrogram that Fig. 2-Fig. 4 is porphyrin, and Fig. 5-Fig. 7 is the ultraviolet-visible light spectrogram, and it is consistent that its characteristic peak and porphyrins feature go out peak, and Fig. 8-Figure 10 is nuclear magnetic resonance spectrum
Figure, synthetic by the analysis showed that porphyrin.
The structural characterization data of the free imidazoles porphyrin of table 1
Porphyrin is to Li/SOCl
2the impact of battery performance
Synthetic porphyrin (3a, 3b, 3c) is quantitatively added to respectively in the electrolytic solution of battery, by battery performance test, obtain Li/SOCl
2the sparking voltage of battery and the relation of discharge time respectively as shown in figure 11, as can be seen from the figure, are compared with blank battery, when free porphyrin joins Li/SOCl
2after in battery electrolyte, increase is in various degree all arranged the discharge time of battery, wherein, discharge time is by blank 1098s, the longest 2010s that extends to, the order of discharge time is 3a>3b>3c>bare battery; In order further to weigh the porphyrin compound catalyzer to Li/SOCl
2the catalytic performance of battery, for Li/SOCl
2the average discharge voltage of battery and energy capacity of battery, we adopt following formula to be calculated:
Battery average voltage: U
av=∑ U Δ t/ ∑ Δ t (1)
Energy capacity of battery: E=∫ Pdt=∫ U
2/ Redt=1/Re ∑ U
2Δ t (2)
The battery relative energy:
(wherein: U: sparking voltage, P: output rating, Δ t: time difference, E: energy capacity of battery, E
0: blank energy capacity of battery)
According to above formula, the battery data of free porphyrin catalysis is calculated, obtain table 2, from Figure 12 and Figure 13, can find out, after adding catalyzer, little for the average discharge voltage impact of battery, basic and blank remains on quite level; But, energy capacity of battery for battery but has raising in various degree, with respect to blank 221mAh, after adding for free porphyrin 3a, 3b, 3c, cell container can reach 445mAh, 382mAh, 302mAh, and amplification reaches 101%, 73%, 37%, to sum up, from discharge time, average discharge voltage, these several respects of cell container, consider, free porphyrin 3a, 3b, 3c are to Li/SOCl
2battery has played katalysis preferably.This reason wherein may be that free porphyrin is at SOCl
2electrolytic reduction in electrocatalysis, changed the passivating conditions of electrode, thereby stoped the formation of LiCl film, therefore can effectively improve the performance of battery.
Table 2 porphyrin catalysis thionyl chloride battery data analysis table
Use first free porphyrin to join Li/SOCl as catalyzer
2in battery electrolyte, measure their sparking voltage to curve discharge time, and calculated average discharge voltage, energy capacity of battery and the relative energy capacity of battery of each battery.Experimental data shows: after above-mentioned several porphyrin compounds are added to battery electrolyte, the prolongation of different time is all arranged the discharge time of battery, and the average discharge voltage of battery is basic and quite blank, and energy capacity of battery has raising by a relatively large margin, wherein, compound 3a demonstrates best catalytic performance.As can be seen here, free porphyrin compound is to Li/SOCl
2battery has catalytic performance preferably, can significantly improve its battery performance.
The above, be only best mode for carrying out the invention, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses, and the simple change of the technical scheme that can obtain apparently or equivalence are replaced and all fallen within the scope of protection of the present invention.
Claims (3)
1. a free porphyrin, is characterized in that, structural formula is:
2. the preparation method of a free porphyrin claimed in claim 1, is characterized in that, comprises the following steps:
The first step, 5-(4-hydroxy phenyl)-10, 15, synthesizing of 20-Triphenylporphyrin (1a), adopt ripe Alder propionic acid method, concrete operation step is: add the 150mL propionic acid in the 500mL three-necked bottle, then phenyl aldehyde 4.60mL (45mmol) and p-Hydroxybenzaldehyde 1.83g (15mmol) are dissolved in respectively in the 10mL propionic acid, be added in three-necked bottle, heating magnetic agitation are fully mixed the two, oil bath is heated to propionic acid and refluxes, slowly in reactor, add 10mL to be dissolved with the propionic acid solution that 4.16mL (60mmoL) newly steams the pyrroles, after dropwising, continue back flow reaction 1 hour, stopped reaction, standing cooling, reduction vaporization, remove the propionic acid solvent, evaporate to dryness as far as possible, add 100mL ethanol in reactor, be put in standing over night in refrigerator, decompress filter, and colourless to filtrate with ice washing with alcohol suction filtration product, obtain the purple solid, the crude product obtained is dissolved with methylene dichloride, chromatographic silica gel is stationary phase, methylene dichloride is eluent, carry out column chromatography for separation, collect the second chromatographic band, obtain target product 1a,
Second step, three kinds contain the synthetic of bromine alkoxyporphyrin (2a, 2b, 2c): with 5-(4-(2-bromine oxethyl) phenyl)-10,15,20-Triphenylporphyrin (2a) synthesize example, concrete operations are: the anhydrous DMF that adds 10ml heavily to steam in the three-necked bottle of 50ml, then by glycol dibromide (0.80ml, 9.6mmol) add wherein, claim anhydrous K
2cO
3(0.40g, 2.89mmol) add wherein, be heated to 80 ℃, compound 1a (0.20g, 0.32mmol) be dissolved in the DMF solution of 5ml, slowly drop in reaction vessel, pass into N2, maintain temperature of reaction at 80 ℃, TLC monitoring reaction process to reaction approaches fully, react 6 hours, stopped reaction, underpressure distillation remove DMF and unreacted complete 1, the 2-ethylene dibromide, obtain thick product, thick product is dissolved in a small amount of trichloromethane, trichloromethane/normal hexane (V/V=5:1) mixed solvent of take is eluent, chromatographic silica gel is that stationary phase carries out the column chromatography for separation purification, collect the first chromatographic band and obtain target product (2a), compound 5-(4-(3-bromine propoxy-) phenyl)-10, 15, 20-Triphenylporphyrin (2b) and 5-(4-(4-bromine butoxy) phenyl)-10, 15, synthesizing of 20-Triphenylporphyrin (2c) is similar to the preparation process of compound (2a), just by reaction raw materials 1, the 2-ethylene dibromide changes respectively 1 into, 3-dibromopropane and 1, the 4-dibromobutane,
The 3rd step, three kinds contain the synthetic of imidazolyl porphyrin (3a, 3b, 3c): 5-[4-(2-imidazolyl)-oxyethyl group] phenyl-10,15, the synthetic concrete steps of 20-Triphenylporphyrin (3a) are: in single neck bottle of 50mL, add 15mL heavily to steam DMF as solvent, by compound 2a (0.10g, 0.13mmol) and imidazoles (0.9g, 13mmol) add wherein, then add anhydrous K
2cO
3(0.50g, 3.6mmol), under room temperature, lucifuge stirs, the process of TLC monitoring reaction is to reacting completely, react 20 hours, DMF is removed in underpressure distillation, then the mixture of reaction is dissolved in the trichloromethane of 20mL, be washed till neutrality with the distilled water of 20mL, after extraction, the decompression rotary evaporation, concentrate to obtain thick product, then take chromatographic silica gel as stationary phase, trichloromethane/ethanol (V/V=20:1) carries out column chromatographic isolation and purification for eluent, collect the first chromatographic band and obtain target product (3a), compound 5-[4-(3-imidazolyl)-propoxy-] phenyl-10, 15, 20-Triphenylporphyrin (3b) and 5-[4-(4-imidazolyl)-butoxy] phenyl-10, 15, synthetic and the 3a's of 20-Triphenylporphyrin (3c) is synthetic similar, just change respectively reaction raw materials compound 2a into compound 2b and 2c.
3. the described free porphyrin of claim 1 is at preparation Li/SOCl
2application in battery.
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|---|---|---|---|---|
| CN103374004A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Amide porphyrin derivative and preparation method thereof |
| CN105348292A (en) * | 2015-12-02 | 2016-02-24 | 天津工业大学 | Novel NMOFs (PMIL-101(Fe)) drug carrier and preparation method thereof |
| CN105503885A (en) * | 2015-12-02 | 2016-04-20 | 天津工业大学 | Novel NMOFs(IRMOF-3) drug carrier and preparation method thereof |
| CN105732919A (en) * | 2016-03-25 | 2016-07-06 | 同济大学 | Preparation method of porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN112968161A (en) * | 2021-02-01 | 2021-06-15 | 陕西科技大学 | Tetrapyridoporphyrin nickel/active carbon Li/SOCl2Battery carbon anode catalytic material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103374004A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Amide porphyrin derivative and preparation method thereof |
| CN103374004B (en) * | 2013-07-02 | 2016-01-06 | 华南理工大学 | Amide porphyrin derivative and preparation method thereof |
| CN105348292A (en) * | 2015-12-02 | 2016-02-24 | 天津工业大学 | Novel NMOFs (PMIL-101(Fe)) drug carrier and preparation method thereof |
| CN105503885A (en) * | 2015-12-02 | 2016-04-20 | 天津工业大学 | Novel NMOFs(IRMOF-3) drug carrier and preparation method thereof |
| CN105732919A (en) * | 2016-03-25 | 2016-07-06 | 同济大学 | Preparation method of porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN112968161A (en) * | 2021-02-01 | 2021-06-15 | 陕西科技大学 | Tetrapyridoporphyrin nickel/active carbon Li/SOCl2Battery carbon anode catalytic material and preparation method thereof |
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Application publication date: 20130515 |