CN101402728A - Two-dimension netted metal phthalocyanine polymer with controllable bore diameter and uses thereof - Google Patents
Two-dimension netted metal phthalocyanine 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 metal phthalocyanine polymer. The general formula thereof is as shown on the right: M in the formula is transition metal ions or rare-earth ions. The application of the polymer is being 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 metal phthalocyanine 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 lgPt/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 phthalocyanine transition metal complex 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 phthalocyanine, 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 phthalocyanine 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.
Summary of the invention
Technical problem to be solved by this invention provides a kind of two-dimension netted metal phthalocyanine polymer and application thereof of controllable bore diameter, and this polymkeric substance has catalytic activity, better choice and the longer life-span of higher catalytic molecular oxygen.
The two-dimension netted metal phthalocyanine polymer of controllable bore diameter provided by the invention, its structural formula is:
Wherein: M is: transition metal ion or rare earth ion, first-selected Fe, Co, Ru, Pd or La etc.
R is :-N=C (R ')-Ar-(R ') C=N-,-C (R ')=N-Ar-N=(R ') C-,-(R ') C=N-,-N=N-,-O-Ar-O-or-Ar-, wherein, R '=H, Me or Et, wherein-Ar-is:
The complete structure of this two-dimension netted planar metal phthalocyanine polymer can be as follows:
In the formula:
It is metal phthalocyanine complex.
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 phthalocyanine, first-selected conjugated structure.
The two-dimension netted polymkeric substance of controllable bore diameter of the present invention is the novel porous material of a class.Come the aperture of control plane polymkeric substance by the group of introducing different sizes, its objective is that such planar polymer is when the cell catalyst that acts as a fuel uses, its hole (bore portion of network polymer) can be filled 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 that it is planar polymerized, because whole planar polymer molecule forms big ∏ key, and be electronic conductor, the aromaticity of catalyst molecule is stronger, molecule is more stable, so this compounds is expected to realize increasing catalytic activity as the reduction reaction of catalyst molecular oxygen, improve selectivity (the 4e reduction mainly takes place), the purpose that prolongs its work-ing life.
The purposes of planar polymerized phthalocyanine transition metal complex of the present invention is the cell cathode catalyzer that acts as a fuel.
The following description of the preparation method of polymkeric substance of the present invention and performance thereof:
The planar polymerized phthalocyanine that the present invention prepares controllable bore diameter has following five kinds of methods:
Synthetic method skeleton symbol of the present invention is following (in order to write in the easy reaction formula all handles
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) phthalocyanines and aromatic dialdehyde.
2) reaction of four (acyl group) phthalocyanines and aromatic diamines.
3) reaction of four (amino) phthalocyanines and four (acyl group) phthalocyanine
4) four (amino) phthalocyanine is through diazonium salt route and the linked reaction that has the phthalocyanine of active group
5) synthetic by the planar polymerized phthalocyanine of-O-Ar-O-binding
Wherein, reaction formula 5) in MX
2Be metal-salt, as, Fe
2+, Co
2+, Pd
2+Deng muriate or acetate.M is Fe
2+, Co
2+Or Pd
2+Deng metal ion.
Embodiment
[embodiment 1] 2,9,16,23-four (amino) phthalocyanine cobalt synthetic
Three-necked flask at equipment magnetic stirring apparatus, reflux condensing tube, thermometer adds 0.75g (2mmol) 2,9,16, the DMF of 23-four (nitro) phthalocyanine cobalt and 5.76g nine hydrated sodium sulfides and 30ml, heating, slowly stir, when temperature is raised near 60 ℃, accelerates stirring velocity and keep constant temperature 1h, then in the water with reactant impouring 150ml, supernatant liquor is outwelled in centrifugation, the HCL dissolving of 1mol/L, get supernatant liquor, NaOH solution with 2mol/L is neutralized to alkalescence, washs with secondary water washing to be neutral, and suction filtration vacuum-drying obtains product.
2,9,16 of [embodiment 2] other metal-complexing, 23-four (amino) phthalocyanine complex synthetic
2,9,16 of other metal-complexing, synthesizing with embodiment 1 of 23-four (amino) phthalocyanine complex is that 23-four (nitro) phthalocyanine cobalt changes 2,9,16 of other metal ion into 2,9,16, and 23-four (nitro) phthalocyanine complex gets final product.
[embodiment 3] 2,9,16,23-four (ethanoyl) phthalocyanine cobalt synthetic
[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 adds) has bubble to generate, and solution becomes green, after the question response gentleness, promptly obtains Acetyl Chloride 98Min. AlCl
3Mixed solution.
[acetylization reaction of phthalocyanine]
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 phthalocyanine cobalt and the dry CH of 150mL by 0.25mmol
2Cl
2The suspension liquid of forming under agitation, slowly drips the Acetyl Chloride 98Min. AlCl of above-mentioned preparation with dropping funnel
3Mixed solution, 15min adds, and continues stirring at room 2～5h, solution is poured in the frozen water decomposed, and has a large amount of black solids to generate.Filter, use the distilled water wash solid.Obtain black 2,9,16,23-four (ethanoyl) phthalocyanine cobalt solid, productive rate 50%～64%
2,9,16 of [embodiment 4] other metallic ion coordination, 23-four (ethanoyl) phthalocyanine synthetic
2,9,16 of other metallic ion coordination, 23-four (ethanoyl) phthalocyanine synthetic with embodiment 3 just gets final product other metal complexes that the phthalocyanine cobalt changes phthalocyanine into.
[embodiment 5] 2,9,16,23-four (acyl group) phthalocyanine cobalt 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 3.
2,9,16 of [embodiment 6] other metallic ion coordination, 23-four (acyl group) phthalocyanine synthetic
The preparation method just changes the phthalocyanine cobalt into other metal complexes of phthalocyanine with embodiment 3, Acetyl Chloride 98Min. is changed into other acyl chlorides such as propionyl chloride or acyl chlorides and gets final product.
[embodiment 7] 2,9,16, the preparation of the condenses of 23-four (amino) phthalocyanine cobalt and terephthalaldehyde
[method one] is 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, add 2 of 0.5mmol respectively, 9,16,100mL DMSO (processing) solution of 23-four (amino) phthalocyanine cobalt, heating, temperature is controlled at 80 ℃～90 ℃, the acetic anhydride that drips 10mL is to keep acid, the DMSO solution of the 10mL of the terephthalaldehyde of dropping 0.5mmol in 15min, 110 ℃ of insulation 2h change underpressure distillation into, under 100 ℃～110 ℃, steam most of solvent, near doing.Obtain the brown solid, the mixed solution washing with DMF and chloroform obtains product, productive rate 85%～90%
[method two] etc. mol ratio 2,9,16, the DMSO solution of 23-four (amino) phthalocyanine cobalt and terephthalaldehyde adds in the solvent thermal reaction still, in air dry oven, react 24h～48h at 120 ℃～140 ℃, be cooled to room temperature, in reaction mixture impouring cold water, can obtain the brown solid precipitation, suction filtration obtains solid, the solids crude product washs three times with acetone, the DMF of heat respectively, obtains product, productive rate 80%～85%
Its catalytic performance test data 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 0.864V, than 30mV a little less than the Pt/C catalyzer of U.S. E-tek company 30%, than the strong 50mV of simple phthalocyanine 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 phthalocyanine complex at 0.174V in 2mol/L NaOH solution.Electron transfer number is near 4, and behind the reaction 200h, the catalytic performance of measuring catalyzer does not subtract.The little 28.7mW/cm of its monocell maximum power density
2
[embodiment 8] 2,9,16, the preparation of the condenses of 23-four (amino) other metal complexes of phthalocyanine and other aromatic dialdehyde
Synthetic and purification process just changes terephthalaldehyde into other aromatic dialdehyde with embodiment 7, and 2,9,16,23-four (amino) phthalocyanine cobalt changes 2,9,16 into, and other metal complexes of 23-four (amino) phthalocyanine gets final product.
The catalyst oxygen molecule reduction test result of such product preparation is as shown in table 1.
[embodiment 9] 2,9,16, the preparation of the condenses of 23-four (ethanoyl) phthalocyanine cobalt and Ursol D
Reaction unit and method change reaction raw materials into 2,9,16 with embodiment 7, and 23-four (ethanoyl) phthalocyanine cobalt and Ursol D get final product, and separation purification method is with embodiment 7.
Identical among the catalyst oxygen molecule reductive electrocatalysis characteristic of its product preparation and the embodiment 7, test result is as shown in table 1.
[embodiment 10] 2,9,16, the preparation of the condenses of 23-four (acyl group) phthalocyanine cobalt and aromatic diamines
Preparation method and purification process be with embodiment 7, just reaction raw materials changed into other four (acyl group) phthalocyanine and other aromatic diamines gets final product.The preparation of the condenses of other metal complexes and purification process thereof be with embodiment 7, and just the cobalt complex in the raw material changes other metal complexes into and gets final product.
The catalyst oxygen molecule reductive electrocatalysis characteristic test result of its product preparation is as shown in table 1.
[embodiment 11] 2,9,16,23-four (amino) phthalocyanine cobalt and 2,9,16, the preparation of the condenses of 23-four (ethanoyl) phthalocyanine cobalt
Reaction unit, operation steps and product method of purification are with embodiment 7, and just the reaction raw materials terephthalaldehyde changes 2,9,16 into, and 23-four (ethanoyl) phthalocyanine cobalt gets final product.
[embodiment 12] 2,9,16,23-four (amino) other metal complexes of phthalocyanine and 2,9,16, the preparation of the condenses of other metal complexes of 23-four (acyl group) phthalocyanine
Reaction unit, operation steps and product method of purification are with embodiment 7; it is reaction raw materials 2,9,16; 23-four (amino) phthalocyanine cobalt changes 2 into; 9,16, other metal complexes of 23-four (amino) phthalocyanine; terephthalaldehyde is changed into 2; 9,16, other metal complexes of 23-four (acyl group) phthalocyanine gets final product.
Embodiment 10～embodiment 12, the compound that obtains, its catalyst oxygen molecule reductive electrocatalysis characteristic test result sees Table 1.
[embodiment 13] 2,9,16, the preparation of 23-four (diazonium alkali) phthalocyanine cobalt
In the four-hole boiling flask of the 250mL that stirring, reflux condensing tube, thermometer and dropping funnel are housed, add 2 of 0.25mmol, 9,16,23-four (amino) phthalocyanine cobalt is scattered in the suspension liquid of the hydrochloric acid 100mL of 2mol/L, 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 14] 2,9,16, the preparation of 23-four (diazonium alkali) other metal complexes of phthalocyanine
Reaction unit, operation steps and product method of purification are reaction raw materials 2,9,16 with embodiment 13, and 23-four (amino) phthalocyanine cobalt changes 2,9,16 into, and other metal complexes of 23-four (amino) phthalocyanine gets final product.
[embodiment 15] 2,9,16, the preparation (reaction 4) of 23-four (diazonium alkali) phthalocyanine cobalt and the coupled product of the phthalocyanine complex that has active group).
Embodiment 13 obtain 2,9,16, add a little yellow soda ash in the solution of 23-four (diazonium alkali) phthalocyanine cobalt and make solution still be acid reindeer moss,, but then be neutral to Congo red, stir 15min, under agitation be added drop-wise in the phthalocyanine 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 pour in the water, and suction filtration obtains the solids crude product, with difference acetone, DMF cleaning product, obtain coupled product.
The used phthalocyanine complex that has active group in the experiment can be 2,9,16,23-four (amino) phthalocyanine, 2,9,16,23-four (hydroxyl) phthalocyanine and 2,9,16,23-four (alkoxyl group) phthalocyanine.
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 0.0.825V, than 70mV a little less than the Pt/C catalyzer of U.S. E-tek company 30%, than the strong 20mV of simple phthalocyanine complex.Initial reduction potential is compared weak 60mV with the Pt/C catalyzer of U.S. E-tek company 30%, than the strong 30mV of simple phthalocyanine complex at 0.168V 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 22.3mW/cm of its monocell maximum power density
2.
[embodiment 16] 2,9,16, the preparation (reaction 4) of other metal complexes of 23-four (diazonium alkali) phthalocyanine and the coupled product of the phthalocyanine complex that has active group
Reaction unit and operation steps product method of purification are reaction raw materials 2,9,16 with embodiment 15, and 23-four (amino) phthalocyanine cobalt changes 2,9,16 into, and other metal complexes of 23-four (amino) phthalocyanine gets final product.
The catalyst oxygen molecule reduction test result of such product preparation is as shown in table 2.
[embodiment 17] are by the preparation of the planar polymerized phthalocyanine of-O-Ar-O-binding
At the equipment electric mixer, reflux condensing tube, add two (4 successively in the 250ml three-necked flask of electrically heated cover, 4 '-Resorcinol oxygen base) phthalic nitrile 5.0mmol, cobalt chloride 2.5mol, 1, ammediol 40ml is after stirring preheating 10min makes the abundant mixing of medicine, the DBU that adds 1mL is behind back flow reaction 6～8h under 150 ℃～200 ℃ conditions, be cooled to room temperature, obtain black solid, suction filtration with filter cake with acetone be washed till filtrate colourless after, colourless with deionized water wash to filtrate, after the thorough drying, behind the mortar porphyrize, transfer in the beaker, DMF with heat washs three times, suction filtration can obtain the planar polymerized phthalocyanine product, and productive rate is: 47.71%.
Adopting uses the same method can obtain the polymkeric substance of other metallic ion coordination, just cobalt chloride is changed into other metal-salt and gets final product.
Adopt the planar polymerized phthalocyanine of other aryl such as to obtain Ar=thienyl, pyrryl, furyl, ferrocenyl that uses the same method, just two (4,4 '-Resorcinol oxygen base) phthalic nitrile is changed into corresponding raw material and gets final product.
[embodiment 18] are by the preparation of the planar polymerized phthalocyanine of-Ar-binding
Experimental installation and method be with embodiment 17, and (4,4 '-to phenylene) phthalic nitrile gets final product just two (4,4 '-Resorcinol oxygen base) phthalic nitrile to be changed into two.
Can prepare other aryl planar polymerized phthalocyanine with quadrat method.Just (4,4 '-to phenylene) phthalic nitrile changes two into (4,4 '-to arylidene) phthalic nitrile gets final product two.
The catalyst oxygen molecule reduction test result of the product preparation that embodiment 17, embodiment 18 make 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 phthalocyanine 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 1～3, and the catalytic performance of measuring catalyzer behind the catalyzed reaction 200h does not subtract substantially.
The preparation of [embodiment 23] membrane electrodes (MEA)
The employing known method is carried out.Just cathod catalyst adopts the prepared catalyzer of corresponding planar polymerized phthalocyanine title complex of the present invention 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 (the present invention) 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] direct methanol fuel cell (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 (3)
1, a kind of two-dimension netted metal phthalocyanine polymer of 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-or-Ar-, wherein, R '=H, Me or Et, wherein-Ar-is:
2, the two-dimension netted metal phthalocyanine polymer of controllable bore diameter according to claim 1 is characterized in that described M is Fe, Co, Ru, Pd or La.
3, the purposes of the two-dimension netted metal phthalocyanine polymer of the described controllable bore diameter of claim 1 is the cell cathode catalyzer that acts as a fuel.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292623A1 (en) * | 2009-08-26 | 2011-03-09 | Karlsruher Institut für Technologie | Acylated phthalocyanines |
| CN102447115A (en) * | 2010-12-31 | 2012-05-09 | 山东理工大学 | Novel magnesium air battery cathode |
| US8222403B2 (en) | 2009-11-12 | 2012-07-17 | The United States Of America, As Represented By The Secretary Of The Navy | Heteroaromatic phthalonitriles |
| CN106046372A (en) * | 2016-06-29 | 2016-10-26 | 长春理工大学 | Porous reticular conjugated polymer containing phthalocyanine structural unit and preparation method of conjugated polymer |
| CN116925311A (en) * | 2023-09-15 | 2023-10-24 | 厦门凯纳石墨烯技术股份有限公司 | Carbon nano tube/phthalocyanine composite material, preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3723902B2 (en) * | 2003-04-08 | 2005-12-07 | 松下電器産業株式会社 | Electrode for oxygen reduction and electrochemical device using the same |
-
2008
- 2008-11-14 CN CN2008101605631A patent/CN101402728B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2292623A1 (en) * | 2009-08-26 | 2011-03-09 | Karlsruher Institut für Technologie | Acylated phthalocyanines |
| US8222403B2 (en) | 2009-11-12 | 2012-07-17 | The United States Of America, As Represented By The Secretary Of The Navy | Heteroaromatic phthalonitriles |
| CN102447115A (en) * | 2010-12-31 | 2012-05-09 | 山东理工大学 | Novel magnesium air battery cathode |
| CN102447115B (en) * | 2010-12-31 | 2013-08-14 | 山东理工大学 | Magnesium air battery cathode |
| CN106046372A (en) * | 2016-06-29 | 2016-10-26 | 长春理工大学 | Porous reticular conjugated polymer containing phthalocyanine structural unit and preparation method of conjugated polymer |
| CN106046372B (en) * | 2016-06-29 | 2018-05-15 | 长春理工大学 | Holey conjugated polymer of the unit containing phthalocyanine structure and preparation method thereof |
| CN116925311A (en) * | 2023-09-15 | 2023-10-24 | 厦门凯纳石墨烯技术股份有限公司 | Carbon nano tube/phthalocyanine composite material, preparation method and application |
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|---|---|
| CN101402728B (en) | 2010-11-17 |
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