CN1199973C - Substituted carbolnie metal complex and application thereof - Google Patents
Substituted carbolnie metal complex and application thereof Download PDFInfo
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- CN1199973C CN1199973C CNB021353271A CN02135327A CN1199973C CN 1199973 C CN1199973 C CN 1199973C CN B021353271 A CNB021353271 A CN B021353271A CN 02135327 A CN02135327 A CN 02135327A CN 1199973 C CN1199973 C CN 1199973C
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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
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Abstract
The present invention relates to a new substituted porphyrin metal-coordination compound, which is characterized in that the compound has a structure general formula shown as the specification, wherein R1, R2, R3 and R4 respectively represent aromatic substituent radicals, and are identical or different, and M represents transitional metal ions or rare earth ions. The compound is designed and synthesized by simulating biologic enzyme catalysts, and is a nitrogen-containing macrocyclic metal-coordination compound which can catalyze molecular oxygen to generate 4e reduction. The compound can be used as a cathode catalyst for batteries directly using methanol as fuel.
Description
Technical field
The present invention relates to porphyrin metal coordination compound and the application aspect fuel-cell catalyst.
Background technology
Direct methanol fuel cell (Direct Methanol Fuel Cell is called for short DMFC) is that a class can directly utilize methyl alcohol to make the polymer-membrane fuel battery of fuel.Owing to can directly utilize methyl alcohol, need not in the middle of conversion system, have advantages such as system architecture is simple, volume energy density is high, fuel refreshment is convenient.Solved among the PEMFC hydrogen purity is required height, production, accumulating, replenishes inconvenient problem.The methyl alcohol wide material sources, cheap, replenish make things convenient for, be easy to carry, security is improved, available existing domestic fuel is added and military logistics support supply system.Be particularly suitable for removable power supply (power truck, mobile communication etc.), field work, frontier sentry and individual soldier's operation.Cost than the whole fuel cell system of fuel cell of fuel reforming (Reforming) reduces.So DMFC enjoys national governments and scientific worker's attention, become one of fuel cell kind that tool development research is worth.
By development research for many years, DMFC has obtained impressive progress.But the commercialization of DMFC also has many key technical problems that need solution: as, seek cheap, durable catalyzer problem; Methyl alcohol can see through saturating alcohol (Crossover) problem that dielectric film causes; Membrane electrode optimum preparation condition etc.
What the DMFC anode adopted usually is the Pt-Ru/C catalyzer, and negative electrode then is the Pt/C catalyzer, generally adopts the product of E-TAK company and Johnson Matthey company.The research of fuel-cell catalyst is the very interested problem of catalysis expert and operation of fuel cells person always, becomes the research focus.The research of DMFC cathod catalyst mainly contains: precious metal and alloy thereof, as, Pt, Ag, Pt-Mn, Pt-Cr etc.; The sulphur-containing alloys of transition metal.As MRu
5S
5(M=Rh, Re); Special oxide compound, as, perovskite typed, spinel type etc.; Special inorganics.As, pyrrhite etc.; Nitrogenous macrocyclic complex etc.
Because nitrogenous macrocyclic complex is cheap and easy to get, and can anti-methyl alcohol, so this compounds is subject to people's attention as the research of DMFC cathod catalyst.The hot issue of research is: screening of catalyst; Immobilized, pyrolysis, preparation electrode etc.But from existing literature, research is only limited to several simple compounds; Macrocylc compound decomposes after the pyrolysis, is actually atoms metal a small bundle of straw, etc. for silkworms to spin cocoons on and is playing katalysis.Exist catalytic activity not high; Catalyzer is immobilized not firm; Catalytic active component and structure are not clear; Problems such as mechanism is unclear.And precious metal and alloy thereof cost an arm and a leg, and have the problem of inadequate resource.But it causes the performance degradation of negative electrode as the oxidation of cathod catalyst existence catalysis methanol.Transition metal sulphur-containing alloys, transition metal oxide, transition metal salt are studied lessly as cathod catalyst, and its reason may be because their catalytic activity is lower and all can dissolve in acidic medium, makes the cause of catalyst loss.
The research of simulation biological enzyme agent is the advanced subject and the focus of current catalyst science research.The hydrophobic pocket that the interior biological enzyme that plays the catalytic oxidation-reduction effect of organism is formed by protein by its active centre (being connected with the metalloporphyrin title complex of a plurality of electron-donating groups) and periphery is formed, and the pentacoordinate atom of central ion is the nitrogen on the imidazole ring in the protein molecule.Its hydrophobic pocket can prevent the coordination of water molecules and central ion, can improve the selectivity of biological enzyme to the oxygen molecule catalytic reduction greatly like this; The coordination of the nitrogen-atoms of imidazole ring can improve the cloud density of porphyrin ring greatly on a plurality of electron-donating groups that connect on the metalloporphyrin molecule in active centre and the central ion, and its catalytic activity is improved.
The function of fuel battery cathod catalyst is exactly the electro-reduction reaction of catalytic molecular oxygen, i.e. oxygen molecule generation 4e reduction combines with proton produces water.Biological intravital biological enzyme is the reduction of catalytic molecular oxygen equally.So, on the basis of having studied biological enzyme structure and catalytic mechanism, on molecular level, utilize the method for molecular engineering to design compound synthetic and biological intravital oxydo-reductase structural similitude, be used for the performance test of DMFC cathod catalyst, screenability is good, cheap, durable in use, the fuel-cell catalyst of anti-methyl alcohol will be very significant.But the mimic biological enzyme has: oxyphorase, myohaemoglobin, cytochrome c, cytochrome P-450, Terminal oxidase, superoxide-dismutase (SOD) etc.
Summary of the invention
Technical problem to be solved by this invention provides a kind of new purposes of replacement porphyrin metal coordination compound aspect the direct methanol fuel cell catalyzer of simulation biological enzyme.
A kind of replacement porphyrin metal coordination compound of the present invention is characterized in that having following general structure:
In the formula: R
1, R
2, R
3, R
4Be respectively substituting group, can equate also can not wait with aromaticity,
M is transition metal ion or rare earth ion.Preferred Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+
R
1, R
2, R
3, R
4When equating symmetry replacement porphyrin, described substituting group with aromaticity such as substituted-phenyl, substituted heterocycle, substituted naphthyl.
R
1, R
2, R
3, R
4Be asymmetric replacement porphyrin when unequal, described substituting group with aromaticity is substituted-phenyl, substituted heterocycle, substituted naphthyl and with porphyrin ring of aromatic nucleus conjugated link(age) chain, with porphyrin ring of ferrocene conjugated link(age) chain.
The above substituted-phenyl, the substituting group on the phenyl can be selected from H, p-Cl,, p-OCH
3, p-N (CH
3)
2, p-(C
2H
5)
2, p-NO
2, m-NO
2, p-CH
3, p-OH-m-OCH
33,4-(methylene-dioxy), substituted heterocycle can be selected from thiophene, 4-bromothiophene, 4-thiotolene.
Below enumerate the structure of several replacement porphyrins:
1, be symmetric form meta substituted-phenyl porphyrin, have following structure:
The strong electron-donating group of R=, preferred p-N, N-dialkyl amido, p-alkoxyl group or p-alkylthio.
2, have the electron-donating group porphyrin transition metal or the rare-earth ion coordination compound of hydrophobic function for symmetric form, have following structure:
In the formula: X=S, NH, or O, n=1,2,3, R
5=Me, Et (ethyl), n-Pr (n-propyl), or n-Bu (normal-butyl).
3, contain the porphyrin coordination compound of methylthio group for symmetric form, have following structure:
In the formula: M=transition metal ion or rare earth ion; R
6=H, 4-Br, 4-Me, 4-butyl, 4-hexyl.
4, be asymmetric biporphin or many porphyrin transition metals or the rare-earth ion coordination compound that connects by big conjugated link(age), have following structure:
R=H in the formula, Me, Et or other alkyl.
5, be asymmetric conjugation biporphin title complex, have following structure by ferrocene key chain:
R=H in the formula, Me, Et or other alkyl.
Replacement porphyrin coordination compound of the present invention is a simulation biological enzyme agent design synthetic, has catalytic molecular oxygen the nitrogenous Macrocyclic metal complex of 4e reductive takes place.Its purposes is the cathod catalyst that is used for direct methanol fuel cell.
The preparation technology of title complex is:
The first step: the symmetrical porphyrin that (1) meta phenyl derivatives replaces synthetic:
Can adopt improved mixed solvent method to synthesize porphyrin, utilize improved mixed solvent method not only can synthesize the porphyrin compound that is difficult for having strong electron-withdrawing group on the synthetic phenyl ring or has strong electron-donating group with the existing literature method, and synthesized meta (four p-hydroxybenzenes) porphyrin and meta (the four vanilla aldehyde radicals) porphyrin that has hydroxyl on the phenyl ring that literature method can't obtain.Synthesis route is as follows:
In the formula: R '=H, p-Cl,, p-OCH
3, p-N (CH
3)
2, p-N (C
2H
5)
2, p-NO
2, m-NO
2, o-NO2, o-OMe, p-CH
3, p-OH-m-OCH
3, 3,4-(methylene-dioxy) etc.
Synthetic method is:
The mixed solution that in the three-necked flask that has agitator, water trap, reflux condensing tube, adds various lipid acid and oil of mirbane, its ratio is: propionic acid: butyric acid: oil of mirbane: Glacial acetic acid=2: 1: 1: 1 reflux, 30～60min drips the above-mentioned mixed solution of being dissolved in of 40mmol substituted benzaldehyde in 5～30min, in 10～30min, drip the new pyrroles who steams of 40mml (5.36g) be dissolved in above-mentioned mixed solution, solution becomes red-purple, brown, brown to black by yellow.Reflux 0.5～2h 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 of thick product taked different methods according to substituent different in kind. following several method is arranged: (1) column chromatography; (2) select suitable solvent to carry out recrystallization; (3) select after the suitable dissolution with solvents freezing and crystallizing etc.
(2) meta four (substituted heterocyclic radical) porphyrin compound is synthetic
The same the first step of working method (1), just substituted benzaldehyde changes substituted heterocyclic radical formaldehyde into (as, 2 thiophene carboxaldehyde, 4-bromo-2 thiophene carboxaldehyde, 4-methyl-2 thiophene carboxaldehyde, 2-pyrrole aldehyde, 2 furan carboxyaldehydes etc.) get final product, temperature of reaction suitably reduces (110～120 ℃) and is advisable.
The character of the meta heterocyclic porphyrin that makes and the character of meta phenyl porphyrin are similar, and the method for synthetic metal complexes is also similar.Also can utilize directly synthetic its title complex of template.
(3) the asymmetric porphyrin that replaces of meta phenyl derivatives is synthetic: with 5-(4-hydroxy phenyl)-10,15,20-three p-methoxyphenyl porphyrins synthesize example:
Product 5-(4-hydroxy phenyl)-10,15,20-three p-methoxyphenyl porphyrins are isolated from reaction mixture by the method for column chromatography.
Use the same method and can synthesize other asymmetric porphyrin compound:
R
1=R
2=R
3Have following substituting group: p-Cl on the=phenyl ring,, p-N (CH
3)
2, p-N (C
2H
5)
2, o-OMe, 3,4-(methylene-dioxy); Have following substituting group: p-OH, p-NH on the R4=phenyl ring
2, p-SH, p-COOH, o-NH
2, o-OH etc.
R
1=R
3Have following substituting group: p-Cl on the=phenyl ring, p-N (CH
3)
2, p-N (C
2H
5)
2, o-OMe, 3,4-(methylene-dioxy) etc.; Have following substituting group: p-OH, p-NH on the R2=R4=phenyl ring
2, p-SH, p-COOH, o-NH
2, o-OH etc.
R
1=R
2=R
3=2-thienyl, 4-bromo-2-thienyl, 4-methyl-2-thienyl etc.; R
4Have following substituting group: p-OH on the=phenyl ring, p-NH
2, p-SH, p-COOH, o-NH
2, o-OH etc.
Second step: porphyrin transition metal or rare earth ion title complex synthetic
Method 1: the room temperature solid-phase synthesis that adopts porphyrin and metal-salt (excessive slightly)
Solid phase method is compared following advantage with solution method: rejected deleterious organic solvent, be easy to purify (only needing get final product) with the excessive metal-salt of dilute acetic acid solution flush away, easy and simple to handle, synthetic yield is high.
Method 2: adopt template, when synthesizing porphyrin compound, add metal-salt (transition metal salt or rare earth salts) simultaneously with mixed solvent method, the method that employing is treated different things alike as template, helps the formation of big ring with metal ion, can improve the productive rate of title complex greatly, step simplifies the operation.
Concrete operation method is: after the first step (1) drips the pyrroles, in 15min, be cooled to below 80 ℃, add metal-salt, heat up, continue to stir, reflux 20～50min, below the step of its same the first step (1).
The 3rd step: the synthetic of complicated porphyrin can be adopted following method: adopt complicated aromatic aldehyde compound and pyrroles's prepared in reaction 1.; 2. synthesize the porphyrin (as having amino, hydroxyl, sulfydryl etc.) that has active group earlier, and then make with compounds reactions such as haloalkane, acyl chlorides, acid anhydrides.
The complicated group that obtains should have following function: strong electron-donating group, have hydrophobic property.Can guarantee that like this catalytic active center in the metalloporphyrin complex is as being protected in basket.Anti-sealing or hydrophilic compound combine with its active centre, and can only combine with oxygen molecule.Improved complex-catalyzed selectivity.The sub-property of the strong power supply of side-chain radical has improved the catalytic activity of title complex.
Synthesis technique is:
In the formula: X=NH, O, S etc.; R5=Me, Et, n-Pr, n-Bu etc.; Y=Cl, Br, I etc.; N=1,2,3 etc.; M=transition metal ion or rare earth ion (with last same).
Adopt template by the directly synthetic metalloporphyrin complex of aromatic aldehyde, pyrroles and transition metal salt.Because template has the effect of metal ion template, makes the formation of porphyrin ring be more prone to, add above two-step reaction is changed into a step, so the productive rate of the synthetic metalloporphyrin complex of template can improve greatly.And simplified operating procedure.
Coordination compound of the present invention is applied to the cathod catalyst of direct methanol fuel cell, activates immobilizedly during use earlier, makes electrode then.
Advantage of the present invention:
(1) high catalytic activity.Catalyzer with biological enzyme similar structures is expected to have high catalytic activity.
(2) highly selective.Molecular oxygen has two kinds of mechanism when reduction takes place; Also original production H of 2e promptly takes place
2O
2Another kind of mechanism is that also original production water of 4e takes place.But simulation biological enzyme agent highly selective is realized second kind of mechanism, thereby the chemical energy of realizing oxygen is transformed into electric energy fully.
(3) applied widely.Because the agent of simulation biological enzyme does not need pyrolysis to become metal atomic cluster, but stable nitrogenous macrocylc compound, so its use range can be expanded: not only can be used for the fuel cell (pyrolytic porphyrin, phthalocyanine complex are suitable for) of gaseous methanol charging, but also can be used for the DMFC of liquid feeding.The pH scope of Applicable media also broadens.
(4) durable in use.Not as metal atomic cluster, in sour environment, can slowly be dissolved, stable molecular structure can make life of catalyst prolong.
(5) with low cost.Because simulation biological enzyme agent is to adopt transition metal complex, its raw material is easy to get, aboundresources, synthetic route are simple.
(6) alternative noble metal platinum solves precious metal inadequate resource problem.Can replacing of can filtering out act as a fuel usually catalyzer---the platinum of battery.The inadequate resource problem that this not only can solve common used precious metal also can reduce the fuel cell cost, promotes the commercialization of fuel cell.
(7) can anti-methyl alcohol, solve pure problem.Because simulation biological enzyme agent can only redox molecule oxygen, oxidation that can not catalysis methanol so this catalyzer is anti-methyl alcohol, is used such catalyzer can solve pure problem well, thereby is improved the performance of battery greatly.
Embodiment
Embodiment 1:meso-5,10,15,20-four (p-methoxyphenyl) porphyrin synthetic
In the three-necked flask that has agitator, water trap, reflux condensing tube, add 30～60ml propionic acid, 20～30ml butyric acid, 20～30ml oil of mirbane, 20～30ml Glacial acetic acid reflux, 30～60min and in 5～30min, drip 30～60ml propionic acid solution of 40mmol aubepine, drip 30～60ml nitrobenzene solution of the new pyrroles who steams of 40mml (5.36g) in 10-30min, solution becomes red-purple, brown, brown to black by yellow.Reflux 0.5-2h gets dark solution, leaves standstill cool overnight, and suction filtration gets black powder.Use secondary water, absolute ethanol washing gets black-and-blue crystal.
Thick product carries out column chromatography, fills out post with silica gel, makes eluent with methylene dichloride, crosses post and obtains pure product for twice.
Embodiment 2: it is synthetic that other meta symmetry tetra-substituted phenyl porphyrin reaches
The refining of thick product taked different methods according to substituent different in kind. and overview gets up to have following several method: (1) column chromatography; (2) select suitable solvent to carry out recrystallization; (3) select after the suitable solvent pyrolysis freezing and crystallizing etc.
Embodiment 3:meso-5,10,15,20-four (p-methoxyphenyl) ferrous porphyrin (II) title complex synthetic
Solid-phase synthesis: get meso-5,10,15, the ferrous ammonium sulphate of 20-four (p-methoxyphenyl) porphyrin 0.1mol and 0.12mol mixes, and at special grinding machine for grinding 20～50min, washs three times to remove excessive metal-salt with hot dilute acetic acid solution.Thick product separates with column chromatogram chromatography, adopts neutral alumina or silica gel to fill out post, uses CH
2Cl
2, the mixed solvent of sherwood oil carries out wash-out, gets required component.Cross three posts and get pure product.
Embodiment 4: other porphyrin transition metal complexes synthetic
Working method is identical with embodiment 3, just (meso-5,10,15,20-four p-methoxyphenyls) porphyrin is changed into other porphyrin, and ferrous ammonium sulphate changes excessive slightly transition metal salt (or rare earth salts) into and gets final product, and other is operated with embodiment 3
Embodiment 5:meso-5,10,15,20-four (β-ethane oxygen carbonyl ethoxyl phenenyl) ferrous porphyrin (II) synthetic
0.01mol meso-5,10,15,20-four (p-hydroxybenzene) ferrous porphyrin (II) is dissolved among the 30ml DMF, adds baked K
2CO
3(0.1mol) stir, under nitrogen protection, be warming up to 60 ℃, stir 0.5h, drip the 20mlDMF mixed solution of the bromoethyl acetate of 0.01mol, reaction 3h is chilled to room temperature, to going into saturated aqueous common salt (70ml), leaves standstill, filters, and the gained solid is dissolved in CHCl
3, to wash 3 times with secondary water washing, chloroform layer is used the sherwood oil recrystallization after concentrating, and gained purple solid silica gel column chromatography is used the chloroform give eluent, collects first green band, concentrates back sherwood oil recrystallization, gets purple crystals, yield 73%
Embodiment 6: other has polysubstituted metalloporphyrin complex synthetic of hydrophobic group
Operation is meso-5 with embodiment 5, and 10,15,20-four (p-hydroxybenzene) ferrous porphyrin (II) changes meso-5 into, 10,15, other metal complexes or the rare earth compounding of 20-four (p-hydroxybenzene) porphyrin, or change meso-5 into, 10,15, other metal complexes of 20-four (p-aminophenyl) porphyrin or rare earth compounding etc. change bromoethyl acetate into bromo (chloro) ethyl propionate to get final product, and other is operated with embodiment 5.
Embodiment 7: terephthalaldehyde and meso-5-p-amino phenyl-10,15, and 20-triphenyl ferrous porphyrin (II) Schiff alkali synthetic:
0.2mol meso-5-p-amino phenyl-10,15,20-triphenyl ferrous porphyrin (II) is dissolved in the chloroform of 40ml, adds the baked K of 1mol
2CO
3Heating drips the terephthalaldehyde of 0.1mol and the chloroform mixed solution of 30ml behind the stirring 0.5h, heating, back flow reaction 8h, obtain atropurpureus solution, standing over night, suction filtration obtains the atropurpureus crystal, crystal chloroform recrystallization, single step purification can adopt column chromatography to the greatest extent, obtains product (productive rate 82%).
Embodiment 8: other is synthetic by the biporphin title complex of Schiff alkali key chain
Operation is with embodiment 7; just meso-5-p-amino phenyl-10; 15; 20-triphenyl ferrous porphyrin (II) changes meso-5-p-amino phenyl-10 into; 15, other metal of 20-triphenyl porphyrin or the title complex of rare earth ion change terephthalaldehyde into 1; the compound that 1 '-diacetyl ferrocene etc. have carbonyl gets final product, and other is operated with embodiment 7.
Embodiment 9: sulfur-bearing metalloporphyrin complex synthetic
Operation is with embodiment 1, just its proportioning of solvent employing propionic acid+butyric acid+oil of mirbane is 2: 2: 1, and service temperature is controlled at 120 ℃, and aubepine changes 2 thiophene carboxaldehyde, 4-bromo-2 thiophene carboxaldehyde into, 4-methyl-2 thiophene carboxaldehyde gets final product, and other is operated with embodiment 1.
Embodiment 9: catalyzer immobilized
Take by weighing 0.05g gac Vulcan XC-72 and measure the loading capacity of gac this solvent with suitable solvent.With the solvent pyrolysis 0.01g terephthalaldehyde and the meso-5-p-amino phenyl-10,15 of measured quantity, 20-triphenyl ferrous porphyrin (II) Schiff alkali adds in the 0.05g gac, stirs, leaves standstill aging for some time, and heating steams solvent, decompressing and extracting.
The solid support method of other metalloporphyrin complex is with embodiment 9, and just terephthalaldehyde and meso-5-p-amino phenyl-10,15,20-triphenyl ferrous porphyrin (II) Schiff alkali changes into needs immobilized metalloporphyrin complex to get final product.
Embodiment 10: the solid support method of other gac
The immobilized method of other gac just changes gac Vulcan XC-72 into BP2000 with embodiment 9, homemade mahogany gac, and expanded polypropylene nitrile pyrolyzate etc. gets final product.
Embodiment 11: the activation of catalyzer
9 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 12: the electrochemical properties of metalloporphyrin complex is measured
The electrocatalysis characteristic test of catalyzer adopts Dutch AutoLab electrochemistry integrated test system to finish, and cyclic voltammetric adopts three-electrode method to measure, platinum is made the research electrode, and another platinized platinum is made supporting electrode, and Ag-AgCl makes reference electrode, make solvent with the DMSO behind the purifying, (Bu
4N) ClO
4Make supporting electrolyte, measure terephthalaldehyde and meso-5-p-amino phenyl-10,15, the dilute solution (～10 of 20-triphenyl ferrous porphyrin (II) Schiff alkali
4Mol/l) cyclic voltammetry curve, the scanning current potential is-2V～1.2V that sweep velocity 400mV/s scanned for 5 weeks.
From oxidized under different potentials, the reductive situation of the cyclic voltammetry curve that obtains metalloporphyrin complex to be determined as can be seen, can obtain the electrochemical properties of this compound thus.
Embodiment 13: 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 14: 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 (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. 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, the hot pressing certain hour makes 3cm under certain pressure, the certain temperature
2Membrane electrode.Electrode takes out activation, carries out the discharge performance test on fuel battery test platform.
Test result shows: the open circuit voltage of battery is identical or close with the open circuit voltage of the Pt/C cathod catalyst of using Johnson Matthey company and E-Tek company.The discharge curve of battery is better than the result of the report [15] 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 CO outward
2Wait other product, illustrate that such catalyzer is anti-methyl alcohol.Eliminated because the cathode performance decay that saturating alcohol causes.
Immobilized and activation method:
Take by weighing 0.05g gac (Vulcan XC-72, BP2000, homemade mahogany gac, expanded polypropylene nitrile pyrolyzate etc.) and measure the absorption situation of gac this solvent with suitable solvent.With the immobilized catalyst precursor of a certain amount of needs of solvent pyrolysis of measured quantity, add in the 0.05g gac that takes by weighing, stir, leave standstill aging for some time, heating steams solvent, decompressing and extracting.The activation of the catalyzer that gac is immobilized is adopted under argon shield, heats up 1 ℃/min of heat-up rate 300～900 ℃ of following activation procedure
The preparation of membrane electrode and battery performance test
Employing is coated with the cream method:
Take by weighing a certain amount of anode catalyst Pt-Ru/C (Johnson Matthey company), gac (Vulcan XC-72, BP2000 etc.), Nafion emulsion (Adrich company, 5% emulsion) (or polyaniline, polypyrrole etc.) mix in certain amount of solvent (low-carbon alcohol or water), disperse 30～70min with ultrasonic disperser, in baking oven, dry by the fire to suspension liquid and become paste, cover with paint, lacquer, colour wash, etc. the Nafon 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 adopt the immobilized activation back of title complex of the present invention 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.Take out activation, on fuel battery test platform, carry out the discharge performance test.
Test result shows: the open circuit voltage of battery is identical or close with the open circuit voltage of the Pt/C cathod catalyst of using Johnson Matthey company and E-Tek company.The discharge curve of battery is better than the report of S.Gupta et al, and cathode reactant detect to be found (with the online detection of gas-chromatography), cathode reactant dewater and methyl alcohol outside do not find CO
2, other methanol oxidation product such as formaldehyde, formic acid, illustrate that such catalyzer is anti-methyl alcohol.Eliminated because the cathode performance decay that saturating alcohol is caused.
Claims (6)
1, a kind of purposes of replacement porphyrin metal coordination compound of following general structure is the cathod catalyst that is used for direct methanol fuel cell:
In the formula: R
1, R
2, R
3, R
4Be respectively substituting group with aromaticity,
R
1, R
2, R
3, R
4When equating, be that symmetry replaces porphyrin, described substituting group with aromaticity is substituted-phenyl or substituted heterocycle, substituted-phenyl wherein, and the substituting group on the phenyl is selected from H, p-Cl,, p-OCH
3, p-N (CH
3)
2, p-(C
2H
5)
2, p-NO
2, m-NO
2, p-CH
3, p-OH-m-OCH
3Or 3,4-(methylene-dioxy), substituted heterocycle is selected from thiophene, 4-bromothiophene or 4-thiotolene;
R
1, R
2, R
3, R
4When unequal, be asymmetric replacement porphyrin, described substituting group with aromaticity is substituted-phenyl, substituted heterocycle or with porphyrin ring of aromatic nucleus conjugated link(age) chain, with porphyrin ring of ferrocene conjugated link(age) chain, substituted-phenyl wherein, the substituting group on the phenyl is selected from H, p-Cl,, p-OCH
3, p-N (CH
3)
2, p-(C
2H
5)
2, p-NO
2, m-NO
2, p-CH
3, p-OH-m-OCH
3Or 3,4-(methylene-dioxy), substituted heterocycle is selected from thiophene, 4-bromothiophene or 4-thiotolene;
M is transition metal ion or rare earth ion, is selected from Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+
2, the purposes of compound according to claim 1 is characterized in that described compound is a symmetric form meta substituted-phenyl porphyrin, has following structure:
R=p-N, N-dialkyl amido, p-alkoxyl group or p-alkylthio.
3, the purposes of compound according to claim 1 is characterized in that described compound is electron-donating group porphyrin transition metal or the rare-earth ion coordination compound that symmetric form has hydrophobic function, has following structure:
In the formula: X=S, NH, or O, n=1,2,3, R
5=Me, Et, n-Pr, or n-Bu;
M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+
4, the purposes of compound according to claim 1 is characterized in that described compound is the porphyrin coordination compound that symmetric form contains methylthio group, has following structure:
In the formula: M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+R
6=H, 4-Br, 4-Me, 4-butyl, 4-hexyl.
5, the purposes of compound according to claim 1 is characterized in that described compound is asymmetric biporphin transition metal or the rare-earth ion coordination compound that connects by big conjugated link(age), has following structure:
R=H in the formula, Me, Et;
M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+
6, the purposes of compound according to claim 1 is characterized in that described compound is asymmetric conjugation biporphin title complex by ferrocene key chain, has following structure:
R=H in the formula, Me, Et;
M=Fe
3+, Fe
2+, Co
2+, Ni
2+, Cu
+, Cu
2+, Ru
3+, Pd
2+, Mn
2+, Mo
3+, La
3+, Ce
3+Or Yb
3+
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|---|---|---|---|
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|---|---|---|---|---|
| TWI609719B (en) * | 2016-12-09 | 2018-01-01 | National Taiwan University Of Science And Technology | Catalyst for fuel cell and method for manufacturing the same |
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| 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI609719B (en) * | 2016-12-09 | 2018-01-01 | National Taiwan University Of Science And Technology | Catalyst for fuel cell and method for manufacturing the same |
| US10529993B2 (en) | 2016-12-09 | 2020-01-07 | National Taiwan University Of Science And Technology | Catalyst for fuel cell and method for manufacturing the same |
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| CN1472212A (en) | 2004-02-04 |
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