CN101402727B - Two-dimension netted metalloporphyrin polymer with controllable bore diameter and uses thereof - Google Patents
Two-dimension netted metalloporphyrin polymer with controllable bore diameter and uses thereof Download PDFInfo
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Abstract
The invention provides a controllable pore diameter two-dimensional reticular plane metalloporphyrin polymer. The general formula thereof is as shown on the right: M in the formula is transition metal ions or rare-earth ions. The polymer is used as a catalyst for the cathode of a fuel cell.
Description
Technical field
The present invention relates to mesh structural porous material and application thereof with the metalloporphyrin polymer formation.
Background technology
The colleague is consistent both at home and abroad thinks, the biggest obstacle of fuel cell industrialization is expensive and low durability (also having other problem to need to solve certainly).In high cost, for efficient, steady running, a large amount of platinum catalysts that use occupy than large portion in membrane electrode (MEA).According to the literature, reach optimum efficiency, the used in amounts offer 1gPt/kW of platinum.In addition, also there is resource-constrained problem in platinum catalyst.Can implement in order to have addressed this problem two schemes: one, the utilization ratio of raising platinum, the consumption of reduction platinum, USDOE target in 2010 is 0.2gPt/kW.But along with the reduction of platinum carrying capacity, the efficient of battery can reduce, and the life-span can shorten; Its two, adopt non-platinum group catalyst.In the long run, the basic outlet that adopts non-platinum group catalyst to be only to address this problem.So the act as a fuel research of cell cathode catalyzer is subject to people's attention (R.Jasinski.Nature, 1964,201,1212 as the porphyrin transition metal complexes of non-platinum group catalyst; J.Kua et al.J Am Chem Soc, 1999,121:10928～10941).The hot issue of research is the selection of porphyrin, immobilized, the activation method of catalyzer, contents such as activity of such catalysts composition, structural analysis and catalytic mechanism.Because the investigator mostly adopts simple metalloporphyrin complex, need carry out pyrolysis processing, macrocylc compound decomposes after the pyrolysis, is actually metal atomic cluster and is playing katalysis.Exist catalytic activity not high, the effective constituent of catalyzer easily runs off, promptly the work-ing life of catalyzer very short, problem (M.Lefevre et al.J Phys Chem, B, 2000,104:11238～11247) such as catalytic active component and structure are not clear, and mechanism is unclear.The catalyst molecular oxygen, what mainly take place is the 2e reduction, wherein, catalytic activity is not high to be the biggest obstacle that runs in its application process.In order to address the above problem, the applicant adopts the method for analogue enztme to prepare a large amount of novel porphyrin title complexs (ZL02135327.1 such as Li Zhongfang, ZL02135326.3, ZL200310114576.6 etc.) and to its catalyst performance study, the catalytic activity of discovering the polymerization metalloporphyrin complex can improve greatly, and the planar polymerized metalloporphyrin complex cell catalyst that acts as a fuel has better activity, higher selectivity and longer life-span.
Summary of the invention
Technical problem to be solved by this invention provides a kind of two-dimension netted metalloporphyrin polymer and application thereof of controllable bore diameter, the especially application aspect fuel-cell catalyst.
The two-dimension netted planar metal porphyrin polymer of controllable bore diameter of the present invention, its general formula is as follows:
The complete structure of its planar polymer can be as follows:
In the formula:
, i.e. metalloporphyrin title complex; M=transition metal ion or rare earth ion etc., first-selected Fe, Co, Ru, Pd or La etc.; R=-N=C (R ')-Ar-(R ') C=N-,-C (R ')=N-Ar-N=(R ') C-,-(R ') C=N-,-N=N-,-O-Ar-O-or-Ar-etc.
Wherein :-Ar-is:
R '=H, Me or Et etc.
Polymkeric substance of the present invention is realized the control in aperture by R group wherein, and it can not be conjugated structure also that the R group can form conjugated structure with porphyrin, first-selected conjugated structure.
When polymkeric substance of the present invention uses at the cell catalyst that acts as a fuel, in its hole (in the porous material molecule) can fill other material, so that have other function of material.As, can allow the Nafion emulsion to enter, can realize the requirement in the membrane electrode preparation process, promptly Catalytic Layer is an electronic conductor, is again proton conductor.
The two-dimension netted polymkeric substance of controllable bore diameter is the novel porous material of a class.Not only itself have catalytic performance, conductivity, and the sky (space, hole) that can uniform distribution varies in size to be realizing other function of material, as, fill other material, filter etc.
The two-dimension netted polymkeric substance that it is planar polymerized, because whole planar polymer molecule forms big П key, and be electronic conductor, the aromaticity of catalyst molecule is stronger, molecule is more stable, so this compounds as the reduction reaction of catalyst molecular oxygen be expected to realize to increase catalytic molecular oxygen catalytic activity, improve selectivity (the 4e reduction mainly takes place), the purpose that prolongs its work-ing life.
The purposes of planar polymerized porphyrin transition metal complexes of the present invention is the cell cathode catalyzer that acts as a fuel.
Below be the preparation method and the performance specification thereof of the two-dimension netted planar metal porphyrin polymer of controllable bore diameter.
Synthesizing of polymer raw:
1, meso-5,10,15,20-four (amino) porphyrin is synthetic
2, meso-5,10,15,20-four (ethanoyl) porphyrin is synthetic
Synthesizing of subject polymer:
The planar polymerized porphyrin that the present invention prepares controllable bore diameter has following five kinds of methods:
Synthetic method skeleton symbol of the present invention following (easy in order to write, equal handle in the reaction formula
Four active groups write a Chinese character in simplified form into one, the plane reticulated structure of its product is write a Chinese character in simplified form into linear structure).
1) condensation reaction of four (amino) porphyrins and aromatic dialdehyde.
2) reaction of four (carbonyl) porphyrins and aromatic diamines.
3) reaction of four (amino) porphyrins and four (carbonyl) porphyrin
4) four (amino) porphyrin is through diazonium salt route and the linked reaction that has the porphyrin of active group
5) preparation of the planar polymerized metalloporphyrin complex of aryl link
Wherein, reaction formula 5) in MX
2Be metal-salt, as, Fe
2+, Co
2+, Ni
2+Deng muriate or acetate.
Embodiment
[embodiment 1] meso-5,10,15,20-four (acetylamino phenyl) Cobalt Porphyrin is 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 respectively and in 5～30min, drip 30～60ml propionic acid solution of 40mmol p-Acetylaminobenzaldehyde, 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 gradually.Reflux 0.5h, reaction solution are cooled to 80 ℃～90 ℃, add the 15mmol Cobaltous diacetate, are warming up to 140 ℃～150 ℃, stir, and back flow reaction 2～4h gets dark solution, leaves standstill cool overnight, and suction filtration gets black powder.Use secondary water, absolute ethanol washing gets black-and-blue crystal product meso-5, and 10,15,20-four (acetylamino phenyl) Cobalt Porphyrin.Productive rate 35%～40%.
Thick product carries out column chromatography, fills out post with silica gel, makes eluent with methylene dichloride, obtains pure product by twice column chromatography.
Meso-5,10,15, other metal ion match of 20-four (acetylamino phenyl) porphyrin synthetic the same just changes Cobaltous diacetate into other acetate and gets final product.
[embodiment 2] meso-5,10,15,20-four (aminophenyl) Cobalt Porphyrin is synthetic
[method one] meso-5,10,15,20-four (acetyl aminophenyl) Cobalt Porphyrin 3～5g 3～5h that joins in 2～3mol/L HCl solution of 50～10mL and stir, refluxes, reaction mixture becomes blue-greenish colour, is neutralized to pH value to 8～9 with the NaOH solution of 2mol/L, there is the blue-greenish colour crystal to separate out in the solution, standing over night, ultrafiltration, solid drying.Use the chloroform give solvent, apparatus,Soxhlet's extracts.Remove solvent and obtain product.Productive rate 89%～92%.
The 500mL four neck flasks that [method two] is being equipped with agitator, thermometer, reflux exchanger, argon gas access tube; after adding the 100mL concentrated hydrochloric acid; add four (4-nitrophenyl) Cobalt Porphyrin after 2.0g makes with extra care; heating under the argon shield, stirring, backflow 60min; under the argon shield, drip the concentrated hydrochloric acid solution (150mL) of tin protochloride 9.025g (40mmol) in the 20min.Be cooled to 70～80 ℃, heating in water bath 30min.Hot water bath is changed to cooling bath gradually, is ice-water bath then, and temperature control is between 0～4 ℃, and is a large amount of with ice.Under argon shield, neutralize with the 125mL strong aqua, the reaction very exothermic, the speed that the ammoniacal liquor of noting slowing down drips should remain a lower temperature in the reaction process.The mixed solution of gained is filtered, obtain green solid,, filter, the pressed powder that obtains, washing, drying with the abundant stirring and dissolving of NaOH solution of 200mL 5%.The chloroform give solvent, apparatus,Soxhlet's extracts.Remove solvent and obtain product.Productive rate 80%～85%.
The meso-5 of [embodiment 3] other metal-complexing, 10,15,20-four (acetylamino phenyl) metalloporphyrin complex synthetic
The meso-5 of other metal-complexing, 10,15,20-four (acetylamino phenyl) porphyrin synthetic with embodiment 2, be meso-5,10,15,20-four (acetylamino phenyl) Cobalt Porphyrin changes the meso-5 of other metal ion into, 10,15,20-four (acetylamino phenyl) metalloporphyrin complex gets final product.
[embodiment 4] meso-5,10,15,20-four (acetyl phenyl) Cobalt Porphyrin
Prepare Acetyl Chloride 98Min. AlCl earlier
3Mixed solution:
In the there-necked flask of the 250mL that electric mixer, reflux condensing tube (being furnished with drying tube), dropping funnel are housed, add 60g～90g AlCl
3Be suspended in 100mL exsiccant CH
2Cl
2In, under agitation, drip new 30mL～62mL Acetyl Chloride 98Min. and the 150mL exsiccant CH that steams
2Cl
2The mixed solution of forming (about 10min) has bubble to generate, and solution becomes green, after the question response gentleness, promptly obtains Acetyl Chloride 98Min. AlCl
3Mixed solution.
The acetylization reaction of metalloporphyrin complex:
In the four-hole neck flask of the 500mL that electric mixer, reflux condensing tube (being furnished with drying tube), dropping funnel and thermometer are housed, add meso-5 by 0.25mmol, 10,15, the dry CH of 20-four (phenyl) Cobalt Porphyrin and 150mL
2Cl
2The solution of forming under agitation, slowly drips the Acetyl Chloride 98Min. AlCl of above-mentioned preparation with dropping funnel
3Mixed solution added in 15 minutes, continued stirring at room 2～5h, solution is poured on ice decomposed, and had a large amount of bluish voilet solids to generate.Filter, use the distilled water wash solid.Obtain bluish voilet meso-5,10,15,20-four (acetyl phenyl) Cobalt Porphyrin solid, productive rate 50～60%
The meso-5 of [embodiment 5] other metallic ion coordination, 10,15,20-four (acetyl phenyl) metalloporphyrin complex synthetic
With embodiment 4, just meso-5,10,15, other metal complexes that 20-four (acetyl phenyl) Cobalt Porphyrin changes phthalocyanine into gets final product.
[embodiment 6] meso-5,10,15,20-four (acyl group phenyl) Cobalt Porphyrin synthetic
The preparation method just changes Acetyl Chloride 98Min. other acyl chlorides such as into propionyl chloride or butyryl chloride and gets final product with embodiment 4,5.
The meso-5 of [embodiment 7] other metallic ion coordination, 10,15,20-four (acyl group phenyl) porphyrin synthetic
With embodiment 4,5, just meso-5,10,15,20-four (acyl phenyl) Cobalt Porphyrin changes meso-5 into, and 10,15, other metal complexes of 20-four (acyl phenyl) porphyrin changes Acetyl Chloride 98Min. into other acyl chlorides such as propionyl chloride, butyryl chloride and gets final product.
[embodiment 8] meso-5,10,15, the preparation of the condenses of 20-four (aminophenyl) Cobalt Porphyrin and terephthalaldehyde
[method one] adds the meso-5 of 0.5mmol in the four-hole boiling flask of the 250mL that stirring, reflux condensing tube (drying tube is equipped with in the upper end), thermometer and dropping funnel are housed, 10,15,100mL chloroform (processing) solution of 20-four (aminophenyl) Cobalt Porphyrin, heating, reflux, the acetic anhydride that drips 10mL is to keep acid, the chloroformic solution of the 10mL of the terephthalaldehyde of dropping 0.5mmol in 15min, backflow 2h, change water distilling apparatus into, steaming most of solvent.Obtain the chocolate solid,, obtain product, productive rate 85%～90% with the chloroform washing.
[method two] etc. the meso-5 of mol ratio, 10,15, the chloroformic solution of 20-four (aminophenyl) Cobalt Porphyrin and terephthalaldehyde adds in the solvent thermal reaction still, reacts 24h～48h at 120 ℃～140 ℃ in air dry oven, be cooled to room temperature, reaction mixture cool off, suction filtration, obtain the brown solid, the solids crude product washs three times under heating condition with acetone, chloroform respectively, obtain product, productive rate 80%～85%.
Its catalytic performance of catalyzer of such product preparation is: the reduction of catalyst oxygen molecule, initial reduction potential in the sulphuric acid soln of 1mol/L is at 0.856V, than 40mV a little less than the Pt/C catalyzer of U.S. E-tek company 30%, than the strong 40mV of simple metalloporphyrin complex.Initial reduction potential is compared weak 20mV with the Pt/C catalyzer of U.S. E-tek company 30%, than the strong 60mV of simple metalloporphyrin complex at 0.171V in 2mol/L NaOH solution.Electron transfer number is near 4, and the catalytic performance of measuring catalyzer behind the 200h does not subtract.The little 101mW/cm of its monocell maximum power density
2
[embodiment 9] meso-5,10,15, the preparation of the condenses of 20-four (aminophenyl) other metal complexes of porphyrin and other aromatic dialdehyde
Synthetic and purification process just changes terephthalaldehyde into other aromatic dialdehyde with embodiment 8, meso-5, and 10,15,20-four (aminophenyl) Cobalt Porphyrin changes meso-5 into, and 10,15, other metal complexes of 20-four (aminophenyl) porphyrin gets final product.
The catalyst oxygen molecule reductive test result of such product preparation is as shown in table 1.
[embodiment 10] meso-5,10,15, the preparation of the condenses of 20-four (acetyl phenyl) Cobalt Porphyrin and Ursol D
Reaction unit and method change reaction raw materials into meso-5 with embodiment 8, and 10,15,20-four (acetyl phenyl) Cobalt Porphyrin and Ursol D get final product, and separation purification method is with embodiment 8.
[embodiment 11] meso-5,10,15, the preparation of the condenses of 20-four (acyl group phenyl) other metal complexes of porphyrin and aromatic diamines
Preparation method and purification process just change reaction raw materials into other meso-5 with embodiment 8, and 10,15,20-four (acetyl phenyl) metalloporphyrin complex and other aromatic diamines get final product.The preparation of the condenses of other metal complexes and purification process thereof be with embodiment 8, and just the cobalt complex in the raw material changes other metal complexes into and gets final product.
[embodiment 12] meso-5,10,15,20-four (aminophenyl) Cobalt Porphyrin and meso-5,10,15, the preparation of the condenses of 20-four (acetyl phenyl) Cobalt Porphyrin
Reaction unit, operation steps and product method of purification are with embodiment 8, and just the reaction raw materials terephthalaldehyde changes meso-5 into, and 10,15,20-four (acetyl phenyl) Cobalt Porphyrin gets final product.
[embodiment 13] meso-5,10,15,20-four (aminophenyl) other metal complexes of porphyrin and meso-5,10,15, the preparation of the condenses of 20-four (acyl group phenyl) other metal complexes of porphyrin
Reaction unit and operation steps product method of purification are with embodiment 8; be reaction raw materials meso-5,10,15; 20-four (aminophenyl) Cobalt Porphyrin changes meso-5 into; 10,15, other metal complexes of 20-four (aminophenyl) porphyrin; terephthalaldehyde is changed into meso-5; 10,15, other metal complexes of 20-four (acyl group phenyl) porphyrin gets final product.
Embodiment 10～embodiment 13, the compound that obtains, its catalyst oxygen molecule reductive electrocatalysis characteristic test result is summarized in the table 1 among the embodiment 9.
[embodiment 14] meso-5,10,15, the preparation of 20-four (diazo phenyl) Cobalt Porphyrin
The meso-5 that in the four-hole boiling flask of the 250mL that stirring, reflux condensing tube, thermometer and dropping funnel are housed, adds 0.25mmol, 10,15, the suspension liquid of the hydrochloric acid 100mL of the 2mol/L of 20-four (aminophenyl) Cobalt Porphyrin, in ice-water bath, temperature is controlled at below 0 ℃, stirs the NaNO that slowly drips 3mol/L down
2Solution 100mL adds in 20min, and insulation reaction 2h treats that solid is dissolved into blackish green solution fully, promptly obtains the diazonium salt product.
[embodiment 15] meso-5,10,15, the preparation of 20-four (diazo phenyl) other metal complexes of porphyrin
Reaction unit and operation steps product method of purification are reaction raw materials meso-5 with embodiment 14, and 10,15,20-four (aminophenyl) Cobalt Porphyrin changes meso-5 into, and 10,15, other metal complexes of 20-four (aminophenyl) porphyrin gets final product.
[embodiment 16] meso-5,10,15, the preparation (reaction 4) of 20-four (diazo phenyl) Cobalt Porphyrin and the coupled product of the metalloporphyrin complex that has active group).
The meso-5 that embodiment 14 obtains, 10,15, add a little yellow soda ash in the solution of 20-four (diazo phenyl) Cobalt Porphyrin and make solution still be acid, but then be neutral, stir 15min Congo red to reindeer moss, under agitation be added drop-wise in the metalloporphyrin complex solution that refrigerative contains reactive group, regulate rate of addition, make the temperature of reaction solution be no more than 10 ℃, insulation reaction 30min, reaction solution is poured in the water, suction filtration obtains the solids crude product, uses acetone, chloroform cleaning product respectively, obtains coupled product.
The used metalloporphyrin complex that has active group in the experiment can be meso-5,10,15,20-four (aminophenyl) metalloporphyrin complex, meso-5,10,15,20-four (hydroxy phenyl) metalloporphyrin complex and meso-5,10,15,20-four (alkoxyl phenyl) metalloporphyrin complex etc.
[embodiment 17] meso-5,10,15, the preparation (reaction 4) of other metal complexes of 20-four (diazo phenyl) porphyrin and the coupled product of the metalloporphyrin complex that has active group
Reaction unit, operation steps and product method of purification are reaction raw materials meso-5 with embodiment 16, and 10,15,20-four (diazo phenyl) Cobalt Porphyrin changes meso-5 into, and 10,15, other metal complexes of 20-four (diazo phenyl) porphyrin gets final product.
Embodiment 16～17, and the catalytic oxygen molecule reduction test result of such product preparation is as shown in table 2.
The preparation of the planar polymerized Cobalt Porphyrin title complex of [embodiment 18] phenylene link
Experimental installation and method are with embodiment 1.Just the raw material p-Acetylaminobenzaldehyde is changed into terephthalaldehyde, reaction raw materials proportioning (acetyl-benzaldehyde): pyrroles=1:1, change (terephthalaldehyde) into: pyrroles=1:2 gets final product.The treatment process of product is that the solid that obtains gets final product with chloroform, washing with acetone respectively.
The preparation of planar polymerized other metal complexes of porphyrin of [embodiment 19] phenylene link
The purification process of experimental installation and method and product is with embodiment 18, and the acetate that just Cobaltous diacetate is changed into other metal gets final product.
[embodiment 20] are by the preparation of planar polymerized other metal complexes of porphyrin of-Ar-base link
The purification process of experimental installation and method and product just changes terephthalaldehyde into other aromatic dialdehyde with embodiment 18, and the acetate that Cobaltous diacetate is changed into other metal gets final product.
Ar=thienyl, pyrryl, furyl, ferrocenyl etc.
Its catalytic performance test result of catalysis by the planar polymerized metalloporphyrin complex product preparation of-Ar-base link is as shown in table 3.
[embodiment 21] Preparation of catalysts method
Adopt known method to carry out immobilized, the activation of catalyzer.
The electrocatalysis characteristic test of [embodiment 22] catalyzer
The electrocatalysis characteristic that adopts known method to carry out catalyzer characterizes.Three-electrode method, employing rotating disk electrode, the polarization curve of testing catalytic modified glassy carbon in acid (or alkalescence) medium carries out data processing.Obtain catalytic catalytic oxygen reductive take-off potential and kinetics current density, thereby obtain the catalytic performance of catalyzer.Experimental result shows that the catalytic performance of catalyzer is better than simple metalloporphyrin complex height, selectivity, and the life-span is longer.
The experimental data test result, the reduction of catalyst oxygen molecule, its result is shown in table 1～table 3, and the catalytic performance of measuring catalyzer behind the catalysis 200h does not subtract substantially.
The preparation of [embodiment 23] MEA (membrane electrode)
The employing known method is carried out.Just cathod catalyst adopts the prepared catalyzer of corresponding planar polymerized metalloporphyrin complex to get final product.
Be coated with the cream legal system and be equipped with membrane electrode, anode adopts the black catalyzer of Pt/Ru, and the Pt carrying capacity is 1.2mg/cm
2, in metal ion, the carrying capacity of metal ion is 1.2mg/cm from controlling catalyst (with the prepared catalyzer of corresponding planar polymerized metalloporphyrin complex) in the negative electrode employing
2The beautiful T-090 carbon paper in east, Nafion117 film, 120 ℃, that 15.5MPa hot pressing 120s makes membrane electrode is standby.
[embodiment 24] DMFC performance test
The employing known method is carried out.The membrane electrode that adopts prepared cathod catalyst has been carried out performance test, and the working conditions of battery is 80 ℃ of service temperatures, methyl alcohol 2mol/L, flow velocity 20mL/min, negative electrode oxygen pressure 0.2MPa, flow velocity 60mL/min.The The performance test results of the battery of its different catalysts preparation is shown in table 1, table 2 and table 3.
Claims (2)
1. the two-dimension netted metalloporphyrin polymer of a controllable bore diameter, its structural formula is:
Wherein: M is transition metal ion or rare earth ion,
R is :-N=C (R ')-Ar-(R ') C=N-,-C (R ')=N-Ar-N=(R ') C-,-(R ') C=N-,-N=N-,-O-Ar-O-,-Ar-or-CH=N-, R ' wherein is H, Me or Et, wherein-Ar-is:
2. the two-dimension netted metalloporphyrin polymer of controllable bore diameter according to claim 1 is characterized in that described M is Fe, Co, Ru, Pd or La.
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