CN1634919A - Use of polymerized phthalocyanine compound as cell cathode catalyst with direct alcohols as fuel - Google Patents
Use of polymerized phthalocyanine compound as cell cathode catalyst with direct alcohols as fuel Download PDFInfo
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- CN1634919A CN1634919A CNA2003101145762A CN200310114576A CN1634919A CN 1634919 A CN1634919 A CN 1634919A CN A2003101145762 A CNA2003101145762 A CN A2003101145762A CN 200310114576 A CN200310114576 A CN 200310114576A CN 1634919 A CN1634919 A CN 1634919A
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Abstract
Polymerized phthalocyanine compound with following general formulas can be used as cell cathode catalyst with direct alcohols as fuel. Polymerized phthalocyanine compound has more atoms which can form big pi bonds, high catalytic activity and high selectivity, and large probability of 4e reduction by catalyzing oxygen for releasing oxygen completely. The compound belongs to non-platinums and alcohol-resistant catalyst.
Description
Technical field
The invention belongs to the polymerized phthalocyanine application of compound, especially be used for direct alcohol fuel battery as catalyzer.
Background technology
Directly alcohol fuel battery (DAFC) is a kind of of low-temperature fuel cell, except advantage with low-temperature fuel cell, a kind of new fuel cell as Proton Exchange Membrane Fuel Cells, directly alcohol fuel battery also has fuel feed, replenishes conveniently, do not need characteristics such as fuel reforming, system architecture be simple, be particularly suitable as removable power supply and little, Miniature Power Unit.Have boundless application prospect and market potential.
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.Fuel-cell catalyst normally adopts noble metal platinum and alloy [Ye S Y, Vijh A K, Dao L H, J.Electrochem.Soc., 1997,144 (1): 90-95], because there is the problem that costs an arm and a leg with inadequate resource in such catalyzer, limited the commercialized development of fuel cell.Moreover, but because the oxidation of platinum catalysis methanol, so, cathod catalyst platinum, but the alcohols that catalysis sees through from anode causes the battery performance decay.For solving pure problem, the anti-catalyst for methanol of platinum group has had bibliographical information [Xing Wei etc., Chinese patent, publication number CN1387273A].Non-platinum group, research cheap and easy to get, anti-catalyst for methanol also have bibliographical information [Sundmacher K, Nowitzki O, Hiffmann U, Chem.Ing.Tech., 1997,69:1143-1146].The inventor once adopted porphyrin, phthalocyanine, big cyclammonium or Schiff (Schiff) bases title complex act as a fuel cell catalyst and patent applied for.Research with the phthalocyanines title complex in the research of non-platinum group catalyst is subject to people's attention [Isaacs M, Aguirre J A, Toro-Labbe A, et al., Electrochim Acta, 1998,43 (12-13): 1821-1827], to be the phthalocyanines title complex as catalyzer have its major cause that raw material is easy to get, industrial production, with low cost, catalytic activity advantages of higher greatly.But, the Phthalocyanine-like Catalysts of existing bibliographical information is the comparatively simple title complex of structure, catalyzer is in activation treatment more than 800 ℃, and its phthalocyanine ring is destroyed substantially, and catalyst active center is cluster compound [the Weng L T.Bertrand P that C, N and metal form, Lalande G, et al.ApplSurface Sci, 1995,84:9-21], exist catalyst activity not high, shortcoming such as stable inadequately.
Summary of the invention
Technical problem to be solved by this invention be utilize intramolecularly can form big π key, the more stable polymerized phthalocyanine compound of electronics is used for the cathod catalyst of direct alcohol fuel battery in the molecule.
The polymerized phthalocyanine compound of following general formula is used for the cathod catalyst of direct alcohol fuel battery.
In the formula: n=0,1,2,3.
X=O; R=H, C1-C8 alkane, aromatic hydrocarbon.
X=N; R=-O
2,-H
2, C1-C8 alkane, aromatic hydrocarbon
X=C; R=C1-C8 alkane, aromatic hydrocarbon.
X=S; R=H, C1-C8 alkane, aromatic hydrocarbon.
XR＝CONH
2
XR=COOR ' (R ' be H, alkane, aromatic hydrocarbon);
M＝Fe，Co，Ni，Mn，Cu，Pt，Ru，Pd。
Above-mentioned general formula is preferred:
n＝0.1
X=O; R=Me, Et, phenyl, benzyl
X=N; R=-O
2,-H
2, two (methyl), two (ethyls), two (phenyl), two (benzyls)
X=C; R=Me, Et, phenyl, benzyl
X=S; R=Me, Et, phenyl, benzyl
XR＝CONH
2
XR=COOR ', R '=H, Me, Et, phenyl, benzyl
M＝Fe，Co，Pt。
The synthetic method of the above-mentioned planar polymerized phthalocyanine of the present invention is that the known kerosene raffinate of employing is the phthalic anhydride Wyler's process synthetic of solvent, temperature of reaction is controlled at 150～250 ℃, reaction 5～10h, the purification of thick product adopts sulfuric acid to dissolve, and dilutes the crystalline method then or with the method purification of column chromatography.The phthalocyanine of different polymerization degree adopts phthalic anhydride and equal four phthalic anhydrides to feed in raw material in strict accordance with the mole proportioning and obtains excessive 10～50 times of urea.
Compound of the present invention (catalyst precursor) still needs to be connected (immobilized) with electronic conductor, activation is made catalyzer afterwards and is used for fuel cell.The preferred graphited gac of electronic conductor, conductive polymers etc., condition optimization rare gas element (argon gas etc.) the atmosphere protection of activation treatment is heat-treated at 200 ℃～1200 ℃ down.Catalyzer after immobilized needs activation, to strengthen the adsorption strength of catalyst precursor on gac, catalyzer is redistributed at activated carbon surface, forms unimolecular layer as far as possible and arranges, thereby increase reactive site.The adsorption strength of all right enhanced activity charcoal of thermal treatment and catalyst precursor, thereby the electroconductibility and the catalytic activity of raising catalyzer.The using method of such catalyzer is identical with fuel battery cathod catalyst commonly used.
The catalytic activity of the catalyzer that makes, selectivity, anti-methyl alcohol performance measurement method and the application method of catalyzer in fuel cell are identical with the measuring method and the using method of custom catalysts.In the metal carrying capacity of negative electrode at 0.1～6mg/cm
2In the scope.
Advantage of the present invention:
The present invention carries out chemically modified to the phthalocyanine ring, the fuel-cell catalyst of the novel non-platinum group of design synthetic from the method employing molecular engineering principle of molecular level utilization simulation biological enzyme.
The structure of The compounds of this invention is the aggretion type phthalocyanine complex, the atomicity that forms the big π key of conjugation in molecule increases, electronics in the molecule is more stable, energy level difference between highest occupied molecular orbital in the molecule (HOMO) and the lowest unoccupied molecular orbital (LUMO) reduces, make the easier electronics that obtains of molecule, also lose electronics easily, the catalyst activity that is used for direct alcohol fuel battery is higher, selectivity is strong, but the 4e reduction takes place in the Catalytic Oxygen molecule, and the chemical energy of oxygen is discharged fully.
Synthetic compound of the present invention is an industrial chemicals cheap and easy to get, and cost is low.
Combine firmly long service life with electronic conductor.
Belong to non-platinum group, the catalyzer of anti-the alcohols.Not only alternative precious metals pt and alloy thereof solve the problem of precious metal inadequate resource, and can solve pure problem, for the commercialization of DMFC provides material guarantee.
Description of drawings
Fig. 1 is six (4-nitro) the dicyclo phthalocyanine cobalts (HNODPcCo) that adopt carbon and the carry graphic representation as cathode in direct methanol fuel cells catalyst characterization battery performance;
Fig. 2 for the dicyclo phthalein cyanogen iron (II) [DPcFe (II)] that adopts carbon and carry as the direct voltage-to-current graphic representation of methanol fuel cell cathode catalyst characterizing battery performance;
Fig. 3 is for methyl alcohol being fuel negative electrode ejecta collection liquid gas-chromatography (GC) detected result;
Fig. 4 is the negative electrode ejecta collection liquid gas-chromatography GC detected result of fuel for Virahol.
Embodiment
Embodiment 1 n=0; X=N, R=-O
2Synthesizing of M=Fe six (4-nitro) dicyclo FePC (II) [HNODPcFe (II)]
In the three-necked flask that agitator, reflux condensing tube, thermometer are housed, add 150mL kerosene raffinate, 15.6g 4-nitro phthalic imidine, 16g urea and 2.95g pyromellitic dianhydride, be heated to 140 ℃, stir 1h, keep 180 ℃ of reaction 4h until mixing.Be cooled to about 80 ℃ and add 16g urea, 0.4g amine molybdate and 10.6g ferrous ammonium sulphate, stir 0.5h.180 ℃ of following stirring reaction 3h.Be cooled to 80 ℃ and add 5g urea, 180～220 ℃ of following stirring reaction 3h.Obtain black particle.Filter thick product.
The purifying of sample adopts the method for concentrated sulfuric acid dissolution and dilute with water, productive rate 53.8%
Its nucleus magnetic resonance diagram data is: 6.95～7.20 (multiplets), 8.07～8.10 (doublets), 8.45～8.62 (triplets), 8.94 (unimodal), 9.66 (unimodal), 10.07～10.18 (bimodal)
Embodiment 2
Among the embodiment 1, substitute ferrous ammonium sulphate with cobalt chloride and can obtain the title complex six that central metallic ions is a cobalt ion (4-nitro) dicyclo phthalocyanine cobalt (II) [HNODPcCo (II)].
Can obtain different metal ionic title complex if substitute ferrous ammonium sulphate with other salt.
Embodiment 3
Among the embodiment 1,, can make the polymerized phthalocyanine title complex of n=1 if the mole proportioning of control 4-nitro phthalic imidine and pyromellitic dianhydride is 4: 1.Its mole proportioning is 10: 3, can obtain the polymerized phthalocyanine title complex of n=2.
Among the embodiment 1,, can obtain six (4-methyl) dicyclo FePC if substitute 4-nitro phthalic imidine with 4-methylphthalic acid acid anhydride.
If adopt the Tetra hydro Phthalic anhydride of other 4 replacements to substitute 4-nitro phthalic imidine, can obtain having other substituent phthalocyanine complex.
Embodiment 5 n=0, XR=COONH
2Synthetic [TCNDPcFe (II)] of six (4-amide group) dicyclo FePCs (II)
Replace 6.47g 4-nitro phthalic imidine with the 10g trimellitic acid 1,2-anhydride, other is operated with embodiment 1, obtains product (black solid) 5.72g, and productive rate is 49.88%.Its
1H NMR (DMSO-d
6) δ
H: 7.82～8.69 (multiplets), 9.20～9.90 (multiplets), 11.57～11.76 (multiplets), 12.28 (singlets).
The immobilized technology of backflow steam seasoning of embodiment 6 catalyst precursors.
In Erlenmeyer flask, add 0.2539g HNODPc Fe (II) and 30mL DMSO heating respectively and make its dissolving.Add the 1.08g gac, sonic oscillation 2h, heating, backflow, stirring 24h.Beaker is put in the mixture taking-up, placed when being evaporated to fast doing on the heating jacket and take off, put into baking oven in 75 ℃ of following ageings, oven dry.
Preparation of catalysts for different catalysts precursor and different carrying capacity thereof can adopt above-mentioned steps to carry out.
The activating process of embodiment 7 catalyzer
Take by weighing a certain amount of catalyzer in porcelain boat, put into electric tube furnace and seal.The flow velocity of adjusting argon gas is 20mL/min, and logical argon gas 0.5h is to eliminate the air (oxygen) in the electric furnace, and beginning is heated to temperature required (200～1200 ℃) according to the temperature programming of setting, and lowers the temperature behind insulation 2～3h.After furnace temperature is cooled to room temperature, take out the activatory samples weighing, the amount of counting loss, it is standby that catalyzer is put into moisture eliminator.
The experiment of embodiment 8 catalyzer electro catalytic activities
Catalyst film is covered with paint, lacquer, colour wash, etc. in the glass-carbon electrode surface as working electrode, and Ag/AgCl (saturated KCl solution) electrode is a reference electrode, and platinum filament is a counter electrode.Adopt three-electrode method, experimentize with 263 potentiostats, 616 rotating disk electrodes.At the aqueous solution of different pH, under the saturated situation of oxygen, rotating disk electrode is measured polarization curve or cyclic voltammetry curve under different rotating speeds.Numerical values recited with the reduction current density of its oxygen characterizes activity of such catalysts.
The catalyzer that the ownership system gets all adopts this method to characterize, and its catalytic activity is the 90%-80% of the 20%Pt carrying capacity of Johnson Metthey company.It is constant substantially to add its reduction current density of methyl alcohol (concentration reaches about 6%) in the sulphuric acid soln.
Embodiment 9 DAFC performance tests
The cream method that is coated with is adopted in the preparation of DAFC membrane electrode, and anode catalyst adopts commercially available (Johnson Metthey company) 20%Pt/C catalyzer, and the platinum carrying capacity is 2mg/cm
2, adopting cobalt contents is that 10% carbon carries six (4-nitro) dicyclo phthalocyanine cobalt, carries 400 ℃ of active processing, negative electrode cobalt carrying capacity is 1.22mg/cm
2, adopt the Nafionl15 film of E.I.Du Pont Company, the T-060 carbon paper of toray company.It is an amount of to get cathod catalyst of the present invention, add suitable quantity of water and Virahol, ultra-sonic oscillation 10～55min, Nafion (perfluorinated sulfonic acid polymer) emulsion and 1～6 10%PTFE (tetrafluoroethylene) emulsion of adding 0.1～2ml 5%, ultra-sonic oscillation 10～50min, at 30 ℃～90 ℃ following solvent flashings, make mixture be paste, lotion is evenly coated on the carbon paper of having handled, dry naturally, in surface spraying one deck Nafion emulsion, make negative electrode.Use the same method and make anode.The dipolar catalyst layer of yin, yang towards the both sides of pretreated Nafion film, at 120 ℃ of following hot pressing (20MPa), 3～4min, is taken out, and it is standby to naturally cool to room temperature.
The mea that makes is dressed up monocell, utilize battery performance testing system to carry out battery performance test.Adopt methyl alcohol to make fuel, the discharge curve of cathod catalyst employing HNODPcFe (II) as shown in Figure 1.
The battery performance test condition is: service temperature is 80 ℃, and methanol concentration is 2mol/l, flow velocity 20ml/min, oxygen pressure 0.15Mpa, flow velocity 60ml/min.
The discharge curve of other alcohols as shown in Figure 2.
The catalytic activity of catalyzer of the present invention is 90～80% of a common Pt/C catalyzer.Selectivity is suitable with the Pt/C catalyzer.
The anti-methyl alcohol performance test of embodiment 10 catalyzer
When battery operated, under frozen water refrigerative condition, collect cathode exhaust gas 1～4h, adopt the mixed liquid of the negative electrode ejecta of collecting gas-chromatography to carry out qualitative and quantitative assay.Adopt the cathode exhaust gas of Pt/C catalyzer to collect the existence that does not detect methyl alcohol (when making fuel) or other alcohol (when making fuel) in the liquid with other alcohol with methyl alcohol.The gas chromatographic detection result that the cell cathode of making fuel with methyl alcohol that HNODPcCo (II)/C makes cathod catalyst and Pt/C is collected liquid as shown in Figure 3, the cell cathode when making fuel with Virahol is collected liquid gas chromatographic detection result as shown in Figure 4.
The performance that is used for cathod catalyst with other catalyzer of compound formation of the present invention is as shown in table 1.
The preparation condition of membrane electrode and the test condition of battery are with shown in the embodiment 9,10.
The battery performance of the different cathod catalysts of table 1 (is fuel with methyl alcohol)
Current density alcohol resistance energy when the open circuit voltage 0.4V of cathod catalyst precursor supported quantity activation temperature battery discharges
Metal/catalyzer (w/w%) ℃ mV mA/cm
2
Six (4-nitro) dicyclo FePC 5 600 0.69 40 is anti-
Six (4-nitro) dicyclo FePC 12 600 0.68 35 is anti-
Six (4-nitro) dicyclo FePC 5 400 0.68 38 is anti-
Six (4-nitro) dicyclo phthalocyanine nickel 8 800 0.65 34 is anti-
Six (4-nitro) dicyclo phthalocyanine platinum 5 600 0.71 86 is anti-
Six (4-methyl) dicyclo FePC 6 400 0.70 52 is anti-
Six (4-sec.-propyl) dicyclo FePC 6 400 0.71 55 is anti-
Six (4-methoxyl group) dicyclo FePC 8 600 0.72 60 is anti-
Six (4-oxygen phenyl) dicyclo FePC 5 600 0.73 61 is anti-
Six (4-dimethylamino) dicyclo FePC 6 400 0.78 62 is anti-
Six (4-dibenzyl amino) dicyclo FePC 5 800 0.79 63 is anti-
Six (4-amido) dicyclo FePC 7 600 0.68 42 is anti-
Six (4-methylthio group) dicyclo FePC 6 400 0.69 54 is anti-
Six (4-methoxycarbonyl) dicyclo FePC 5 400 0.66 44 is anti-
Six (4-carbobenzoxy-(Cbz)) dicyclo FePC 10 400 0.65 38 is anti-
Eight (4-nitro) three ring FePCs 2 600 0.70 69 are anti-
Ten (4-nitro) Fourth Ring FePC 5 800 0.72 74 is anti-
Claims (2)
1, the purposes of the polymerized phthalocyanine compound of following general formula is the cathod catalyst that is used for direct alcohol fuel battery.
In the formula: n=0,1,2,3.
During X=O, R=H, C1-C8 alkane, aromatic hydrocarbon.
During X=N, R=-O
2,-H
2, C1-C8 alkane, aromatic hydrocarbon
During X=C, R=C1-C8 alkane, aromatic hydrocarbon.
During X=S, R=H, C1-C8 alkane, aromatic hydrocarbon.
XR＝CONH
2
XR=COOR ', R ' are H, alkane, aromatic hydrocarbon
M＝Fe，Co，Ni，Mn，Cu，Pt，Ru，Pd。
2, the purposes of the described polymerized phthalocyanine compound of claim 1 is characterized in that:
In the general formula: n=0 or 1
X=O; R=Me, Et, phenyl or benzyl
X=N; R=-O
2,-H
2, two (methyl), two (ethyls), two (phenyl) or two (benzyls)
X=C; R=Me, Et, phenyl or benzyl
X=S; R=Me, Et, phenyl or benzyl
XR＝CONH
2
XR=COOR ', R '=H, Me, Et, phenyl or benzyl
M＝Fe，Co，Pt。
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|---|---|---|---|
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|---|---|---|---|
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| CN1276918C CN1276918C (en) | 2006-09-27 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328193B (en) * | 2007-06-24 | 2010-12-15 | 山东理工大学 | Ferrocene bonding face to face diphthalocyanine complexes and uses thereof |
| CN101327451B (en) * | 2007-06-24 | 2012-01-11 | 山东理工大学 | Uses of planar polymerized phthalocyanine or porphyrin transition metal complexes |
| CN102447115A (en) * | 2010-12-31 | 2012-05-09 | 山东理工大学 | Novel magnesium air battery cathode |
| CN106654465A (en) * | 2015-10-28 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | An electrolyte promoting carbonate decomposition and a lithium-air battery |
| CN106920967A (en) * | 2015-12-27 | 2017-07-04 | 深圳市沃特玛电池有限公司 | A kind of organic method for preparing anode material of high power capacity nanometer |
| CN117543032A (en) * | 2024-01-09 | 2024-02-09 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
-
2003
- 2003-12-31 CN CNB2003101145762A patent/CN1276918C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328193B (en) * | 2007-06-24 | 2010-12-15 | 山东理工大学 | Ferrocene bonding face to face diphthalocyanine complexes and uses thereof |
| CN101327451B (en) * | 2007-06-24 | 2012-01-11 | 山东理工大学 | Uses of planar polymerized phthalocyanine or porphyrin transition metal complexes |
| 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 |
| CN106654465A (en) * | 2015-10-28 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | An electrolyte promoting carbonate decomposition and a lithium-air battery |
| CN106654465B (en) * | 2015-10-28 | 2019-06-21 | 中国科学院宁波材料技术与工程研究所 | Promote the electrolyte and lithium-air battery of carbonate decomposition |
| CN106920967A (en) * | 2015-12-27 | 2017-07-04 | 深圳市沃特玛电池有限公司 | A kind of organic method for preparing anode material of high power capacity nanometer |
| CN117543032A (en) * | 2024-01-09 | 2024-02-09 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
| CN117543032B (en) * | 2024-01-09 | 2024-04-02 | 北京师范大学 | Active functional group-containing MXene-loaded phthalocyanine iron catalyst, and preparation method and application thereof |
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