CN101328192B - Face to face porphyrin dimmer complexe using ferrocene as linker and use thereof - Google Patents
Face to face porphyrin dimmer complexe using ferrocene as linker and use thereof Download PDFInfo
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- CN101328192B CN101328192B CN2007100150776A CN200710015077A CN101328192B CN 101328192 B CN101328192 B CN 101328192B CN 2007100150776 A CN2007100150776 A CN 2007100150776A CN 200710015077 A CN200710015077 A CN 200710015077A CN 101328192 B CN101328192 B CN 101328192B
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- face
- ferrocene
- reaction
- porphyrin
- catalyzer
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- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a face-face dimeric porphyrin complex with ferrocene as a connecting group. The structural formula of the face-face dimeric porphyrin complex is shown on the right, wherein R is H, Me or Et; X is NH, O or S; M is Fe<3+>, Fe<2+>, Co<2+>, Ni<2+>, Ru<3+>, Pd<2+>, Mn<2+>, Mo<3+>, La<3+>, Ce<3+> or Yb; and Y is H, Me, Et, OMe, N(CH3)2 or N(CH2CH3)2. The face-face dimeric porphyrin complex is used for redox reaction, and is taken as a catalyst capable of controlling oxidation reaction, epoxidation reaction and dioxygen reduction reaction, and particularly taken as a cathode catalyst of a fuel cell.
Description
Technical field
The present invention relates to a kind of is the face-face biporphin title complex and the application thereof of linking group with the ferrocene.
Background technology
Synthetic and the catalytic performance research of novel porphyrin transition metal complex is one of important content of mimetic enzyme catalysis agent research, is subjected to scientific worker's attention, becomes the research focus of current catalysis circle.Model system with metalloporphyrin analog cytochrome P-450 monooxygenase is a probe; inquire into the catalysis behavior of monooxygenase in the vital process; illustrating the structure and the function relationship of monooxygenase and open up catalyzed oxidation under the hydro carbons mild conditions from molecular level, is very active subject of domestic and international biomimetic chemistry field.
The research of porphyrin analoglike enzyme catalyst (J P Collman, Science, 1997,275:949-951) be the hot issue of current catalytic field.For this reason, porphyrin class title complex synthetic, particularly face-face biporphin (J M collman, Inorg Chem, 1996,35:6746-6754; J I Sessler, Acc Chem Res, 2001,34:989-997), the ring that many porphyrins form (G M Dubowchik, J Chem Soc, Chem Commun, 1987,293-295) study on the synthesis of title complex becomes the interested problem of people.The synthetic of porphyrin class title complex also provides theoretical basis and material conditions for the research of porphyrin class catalyzer.Systematic study was once done by this seminar of research that face-face biporphin title complex is used for fuel-cell catalyst, as Li Zhongfang etc., Chinese invention patent ZL02135327.1 and ZL02135326.3.
Summary of the invention
Technical problem to be solved by this invention provide a kind of new be the face-face biporphin title complex of linking group with the ferrocene, and in the application in fields such as chemical production field and fuel battery cathod catalyst.
The present invention is the face-face biporphin title complex of linking group with the ferrocene, and its structural formula is:
In the formula: R=H, Me, Et; X=NH, O, S;
M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb;
Y＝H，Me，Et，OMe，N(CH
3)
2，N(CH
2CH
3)
2。
Preferably: R=H, Me;
X＝NH，O，S；
M＝Fe
3+，Fe
2+，Co
2+，Ni
2+，Ru
3+，Pd
2+，Mn
2+；
Y＝H，OMe，N(CH
3)
2，N(CH
2CH
3)
2。
The synthesis technique that the ferrocene key connects face-face biporphin transition metal complex is:
With ferrocene dicarbonyl compound and meso-5-p-amino phenyl-10,15, the synthetic method of the Sciff alkali reduzate of 20-triphenyl porphyrin transition metal complexes condensation is an example.
Ferrocene dicarbonyl compound and meso-5-p-amino phenyl-10,15, the structural formula of the Sciff alkali reduzate of 20-triphenyl porphyrin transition metal complexes condensation is:
The reaction process flow process is:
Concrete synthetic method is with disclosed Li Zhong virtue etc., the content of Chinese invention patent ZL02135327.1 and ZL02135326.3 record.In the technical process the 6th step belongs to catalytic hydrogenation.
Synthesizing of other faces-face biporphin when Y is not H.The at first synthetic active group that has is (as ,-NH
2,-OH ,-SH etc.) and asymmetric metalloporphyrin complex and ferrocene diacetyl (ferrocene dicarbaldehyde, ferrocene two propionyl) carry out condensation reaction and prepare the Schiff alkali cpd, carry out catalytic hydrogenation at last and get final product.
With the ferrocene is the purposes of the face face biporphin title complex of linking group, is the catalyzer that is used for redox reaction, may command oxidizing reaction, epoxidation reaction, molecular oxygen reduction reaction, and the cell cathode catalyzer especially acts as a fuel.
The Preparation of catalysts method can adopt graphited gac, CNT (carbon nano-tube) or metal oxide etc. to adopt methods such as pickling process, backflow pickling process immobilized as carrier.Under argon shield, in electric furnace, activate under the differing temps, obtain needed catalyzer.
Advantage of the present invention:
Face-face biporphin composition catalyst has 2 active centre, can be simultaneously at two Sauerstoffatoms of adsorption of oxygen molecule.The singly-bound that is connected with ferrocene in the molecule can make two distance variables between metalloporphyrin complex by molecular thermalmotion.So more help the single bonded fracture of O-O of oxygen molecule, the 4e reduction takes place, increase selectivity of catalyst, improve energy conversion efficiency thereby improve the catalytic oxygen molecule.
Embodiment
Embodiment 1 ferrocene dicarbonyl compound and meso-5-p-amino phenyl-10,15, the Sciff alkali of 20-triphenyl porphyrin transition metal complexes condensation synthetic.
Ferrocene dicarbonyl compound and meso-5-p-amino phenyl-10,15, the Sciff alkali of 20-triphenyl porphyrin transition metal complexes condensation synthetic.Preceding as described in the present invention 5 steps of reaction process.Concrete synthetic method and Li Zhongfang etc., the disclosed technical scheme of Chinese invention patent ZL02135327.1 and ZL02135326.3.
Embodiment 2 ferrocene dicarbonyl compounds and meso-5-p-amino phenyl-10,15, the reduzate of the Sciff alkali of 20-triphenyl porphyrin transition metal complexes condensation synthetic
It is the 6th step catalytic hydrogenation of reaction process of the present invention.Operation steps is as follows.
The product (product in the 5th step in the reacting flow chart) that takes by weighing among 5～10g embodiment 1 is dissolved among the DMF of 50～150mL, solution is moved in the autoclave of 300mL, the Raney's nickel that adds 2～5g is as catalyzer, feed hydrogen, the pressure of hydrogen is 0.2～0.5MPa, at 50 ℃～130 ℃, stirring velocity is 300～500 commentaries on classics/min reaction 2h～4h down.Stop pressurization, heating, naturally cooling.Reaction solution is taken out, filter away catalyzer.DMF is removed in underpressure distillation.Product carries out recrystallization three times with chloroform, obtains product 3.4g～3.64g, productive rate 68%～72.8%.
Synthesizing of embodiment 3meso-(5-p-hydroxybenzene-10,15,20-three p-methoxyphenyls) porphyrin
Having agitator, water trap, (the best is a propionic acid to add mixed solution with 40～80mlC2～C6 lipid acid in the 500ml three-necked flask of reflux condensing tube, butyric acid, acetate), high boiling derivative (best the is oil of mirbane) reflux 10～60min of 30～60ml with benzene of oxidisability, its mol ratio that drips p-Hydroxybenzaldehyde and aubepine in 5～20min is C2～C6 adipic acid solution of 1:3 (40mmol altogether), drip 40mmol (5.36g) the new pyrroles who steams in 10～30min, solution becomes red-purple by yellow, brown, brown is to black.Reflux 20～80min gets dark solution, leaves standstill cool overnight, and suction filtration gets black powder.Use secondary water, absolute ethanol washing gets black-and-blue crystal.
The refining employing column chromatography method of thick product adopts neutral alumina or silica gel to fill out post, uses DMF, CH
2Cl
2, CHCl
3, ethyl acetate, sherwood oil, the mixed solvent of ether equal solvent or several solvents carries out wash-out, gets required component.Cross post twice, get pure product.Productive rate 8.2%～12.5%
Other contains the synthetic of the asymmetric porphyrin compound of active group embodiment 4
Adopt the method for embodiment 3, aubepine is changed into the N of equimolar amount, N-dimethylaminobenzaldehyde, N, N-diethylin phenyl aldehyde, p-tolyl aldehyde, to aromatic aldehydes such as ethylbenzene formaldehyde then can synthesize the asymmetric porphyrin compound that other contains a hydroxyl.Productive rate 6.8%～12%.
Adopt the method for embodiment 3, substitute p-Hydroxybenzaldehyde, can synthesize and have sulfydryl other asymmetric porphyrin compound as active group with the sulfydryl phenyl aldehyde.
Embodiment 5 contains the synthetic of the asymmetric metalloporphyrin complex of active group
Asymmetric porphyrin compound and Cobaltous diacetate grind 1h down at 40 ℃, and thick product is washed to remove unreacted metal salt with dilute acetic acid.Thick product employing is leant on chromatography method and is separated.Filling out with neutral alumina and to lean on, is elutriant with methylene dichloride and ethanol (6:1), obtains pure product.Productive rate 87%.
Adopt other acetate to substitute Cobaltous diacetate, can prepare other asymmetric metalloporphyrin complex.
The synthetic method and the productive rate thereof of its representational Different Complex are as shown in table 1.
The synthetic situation of the representational asymmetric metalloporphyrin complex of table 1
Embodiment 6 ferrocene groups and active group are the building-up reactions of the asymmetric metalloporphyrin complex of amino
Reactive group prepares Schiff alkali for amino asymmetric metalloporphyrin complex and the condensation reaction of ferrocene diacetyl or ferrocene dicarbaldehyde, Schiff alkali in the reductive reaction process with embodiment 1 and embodiment 2.
Embodiment 7 ferrocene groups and other contain the bonding of active group metalloporphyrin complex
Active group is the asymmetric metalloporphyrin complex of hydroxyl and the key of ferrocene, be to adopt ferrocene two (2-monochloroethane) and hydroxyl asymmetric metalloporphyrin complex under the Anhydrous potassium carbonate katalysis, backflow, stirring reaction 5h obtain in chloroform, and the mole proportioning of two kinds of reactants is 1:2.Product carries out recrystallization with chloroform, separates with chromatography column at last.Get final product.Reaction result is as shown in table 2.
Same method can prepare the compound of the structural formula of X=S in the structural formula.Just get final product with the alternative asymmetric metalloporphyrin complex of hydroxyl of the asymmetric metalloporphyrin complex of sulfydryl.Reaction result is as shown in table 2.
Synthetic result is as shown in table 2.
Embodiment 8 catalyzer immobilized
Take by weighing 0.5～1g gac Vulcan XC-72 and measure the loading capacity of gac this solvent with suitable solvent.Dissolution with solvents 0.1～0.2g compound 2A1 (compound of correspondence in the table 2) with measured quantity adds in the gac, stirs, leaves standstill aging for some time, and heating steams solvent, decompressing and extracting.
The solid support method of other compound is with embodiment 8, and just 2A1 being changed into needs immobilized metalloporphyrin complex to get final product.
The method that other gac is immobilized just changes gac Vulcan XC-72 into BP2000, homemade mahogany gac, and expanded polypropylene nitrile pyrolyzate etc. gets final product.
The activation of embodiment 9 catalyzer
8 immobilized embodiment, as to drain catalyzer is under argon shield, at 300～900 ℃ of activation down, temperature programming, 1 ℃/min of heat-up rate, activation 3～5h.Can obtain catalyst activated.
Embodiment 10: the electrocatalysis characteristic of catalyzer is measured
The electrocatalysis characteristic research of catalyzer adopts the general half-cell method of rotating disk electrode to measure.The result shows: catalyzer of the present invention has good catalytic molecular oxygen electric reduction characteristic, than the catalytic activity height of simple single metalloporphyrin complex of bibliographical information.
Embodiment 11 catalyzer are used for epoxidation reaction
In the round-bottomed flask of 250mL, add the 20mL solvent, the catalyzer of 2mmol tetrahydrobenzene and 0.001～0.01mmol, ultrasonic or stirring adds 1mmol PhIO powder down, closed reactor, 20 ℃ of reactions down. reaction 2h～5h is centrifugal with reaction mixture after finishing, to collect clear liquid, add quantitative internal standard substance decane, make GC and analyze. the reaction of different catalysts catalysis cyclohexene oxide generates the productive rate of epoxy cyclohexane as seeing Table 2.
Embodiment 12 catalyzer are used for the catalysis hexanaphthene and prepare pimelinketone
Add solvent benzol 50mL in a small-sized jacketed reactor that can lead to thermostat(t)ed water, each component and concentration thereof are in the reaction system: substrate hexanaphthene 0.02mol/L, iron porphyrin 1 * 10
-4Mol/L, pyridine 5 * 10
-3Mol/L, oxygenant (H
2O
2) be about 0.05mol/L, santochlor 0.1mol/L, consisting of phase-transferring agent (OP-10) 0.004mol/L.Use N before the reaction
2Air in the reactor is caught up with to the greatest extent the induction stirring reaction mixture.When question response reaches balance, the product gas chromatographic analysis.The productive rate of different catalysts catalysis cyclohexane oxidation generation pimelinketone is as shown in table 2.
Embodiment 13 catalyzer are used for Proton Exchange Membrane Fuel Cells (PEMFC)
The preparation of membrane electrode and battery performance test
Employing is coated with the cream method:
Take by weighing anode catalyst Pt/C (Johnson Matthey company) 1～100mg, gac (Vulcan XC-72) 1～50mg, Nafion emulsion (Adrich company, 5% emulsion) 2～30ml, the middle mixing of solvent (low-carbon alcohol or water) that adds 1～50ml, disperse 30～70min with ultrasonic disperser, drying by the fire in baking oven to suspension liquid becomes paste (to need 2～5h) approximately, cover with paint, lacquer, colour wash, etc. on the Nafion film (Nafion112) of treated mistake, the top covers as diffusion layer with carbon paper or carbon cloth; The cream that is coated with of the processing of negative electrode the same (cathod catalyst adopts us to design synthetic, after the immobilized activation with) cathod catalyst is covered with paint, lacquer, colour wash, etc. another side at the Nafion film.Put into mould at thermocompressor, certain pressure (1.0～2.1MPa), certain temperature (120～150 ℃) down the hot pressing certain hour (90～140s), make 4cm
2Membrane electrode.Electrode takes out activation, carries out the discharge performance test on fuel battery test platform.
Test result shows: the peak power of battery is identical or close with the peak power of the Pt/C cathod catalyst of using Johnson Matthey company and E-Tek company, show that cathod catalyst adopts title complex of the present invention to have the catalytic activity identical or close with the Pt catalyzer, is better than other non-platinum group catalyst.
Embodiment 14 catalyzer are used for direct methanol fuel cell (DMFC)
The preparation of membrane electrode and battery performance test
Employing is coated with the cream method:
Take by weighing anode catalyst Pt-Ru/C (Johnson Matthey company) 1～100mg, gac (VulcanXC-72) 1～50mg, Nafion emulsion (Adrich company, 5% emulsion) 2～30ml, the middle mixing of solvent (low-carbon alcohol or water) that adds 1～50ml, disperse 30～70min with ultrasonic disperser, drying by the fire in baking oven to suspension liquid becomes paste (to need 2～5h) approximately, cover with paint, lacquer, colour wash, etc. the Nafion film (Nafion115 of treated mistake, Nafion117 or other proton exchange membrane) on, the top covers as diffusion layer with carbon paper or carbon cloth; The cream that is coated with of the processing of negative electrode the same (cathod catalyst adopts us to design synthetic, after the immobilized activation with) cathod catalyst is covered with paint, lacquer, colour wash, etc. another side at the Nafion film.Put into mould at thermocompressor, hot pressing certain hour under certain pressure, the certain temperature makes the membrane electrode of 3cm2.Electrode takes out activation, carries out the discharge performance test on fuel battery test platform.
Test result shows: the peak power of battery is identical or close with the peak power of the Pt/C cathod catalyst of using Johnson Matthey company and E-Tek company.The discharge curve of battery is better than the results reported of S.Gupta et al, and cathode reactant detects finds (with the online detection of gas-chromatography), and cathode reactant dewaters and methyl alcohol is not found other products such as CO2 outward, illustrates that such catalyzer is anti-methyl alcohol.Eliminated because the cathode performance decay that saturating alcohol causes.
Claims (4)
1. one kind is the face-face biporphin title complex of linking group with the ferrocene, and its structural formula is:
In the formula: R=H, Me, Et; X=NH, O, S;
M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+Or La
3+
Y＝H，Me，Et，OMe，N(CH
3)
2，N(CH
2CH
3)
2。
2. according to claim 1 is the face-face biporphin title complex of linking group with the ferrocene, it is characterized in that, and in the described structural formula, R=H, Me;
X＝NH，O，S；
M＝Fe
3+，Fe
2+，Co
2+，Ni
2+，Ru
3+，Pd
2+，Mn
2+；
Y＝H，OMe，N(CH
3)
2，N(CH
2CH
3)
2。
3. as claimed in claim 1 or 2 a kind of be the purposes of the face-face biporphin title complex of linking group with the ferrocene, it is characterized in that it being to be used for the catalytic oxidation-reduction catalyst for reaction.
4. according to claim 3 is the purposes of the face-face biporphin title complex of linking group with the ferrocene, it is characterized in that it being to be used for fuel battery cathod catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100150776A CN101328192B (en) | 2007-06-24 | 2007-06-24 | Face to face porphyrin dimmer complexe using ferrocene as linker and use thereof |
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|---|---|---|---|
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|---|---|
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| CN101328192B true CN101328192B (en) | 2011-07-20 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382147B (en) * | 2011-09-19 | 2015-01-21 | 济南大学 | Method for preparing ferrocenyl alkynyl porphyrin molecule possessing nonlinear optical activity and application thereof |
| CN105470530B (en) * | 2015-12-27 | 2018-05-08 | 同济大学 | The preparation method of nickel (II) -1,1 '-ferrocenedicarboxylic acid complex elctro-catalyst |
| CN105694526B (en) * | 2016-03-24 | 2017-05-24 | 西北师范大学 | Ferrocene zinc porphyrin organic dye and synthesis as well as application thereof to preparation of dye-sensitized solar cell |
| CN114478654B (en) * | 2021-12-31 | 2024-03-08 | 天津悦泰石化科技有限公司 | Preparation method of ferrocene-porphyrin metal complex, ferrocene-porphyrin metal complex and bimetallic fuel additive |
| CN116333336A (en) * | 2023-05-26 | 2023-06-27 | 潍坊医学院 | Ferrocene-based metal organic framework material and preparation method and application thereof |
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