CN103586063B - Carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst and preparation thereof - Google Patents
Carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst and preparation thereof Download PDFInfo
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Abstract
The invention provides carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst and preparation thereof.Described carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, it is characterized in that, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises material with carbon element 30wt%-90wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 10wt%-70wt%.The present invention is non-precious metal catalyst, by high temperature pyrolysis process, has the pyridine nitrogen of high N-and S-content and graphite nitrogen (Nx-C) composite construction and C-Sn-C structure, significantly improve the catalytic activity to oxygen at alkaline medium System forming.
Description
Technical field
The invention belongs to fuel cell non-precious metal catalyst field, particularly a kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst CuTSPc/C and Synthesis and applications thereof.
Background technology
In recent years, along with development that is economic and society, energy and environment pollution problem increasingly sharpens, and excavation new forms of energy carry out alternative traditional fossil energy becomes the significant problem that 21 century needs solution badly.Wherein fuel cell (FuelCell) is a kind of TRT chemical energy be stored in fuel and oxidant being converted into electric energy by electrochemical reaction, because having energy-efficient, high power density and the low emission even feature such as zero-emission, be considered to the cleaning of 21 century first-selection, efficiently environmental protection power supply [EnergyEnviron.Sci., 4,3167 (2011)].Wherein, platinum (Pt) catalyst has very high catalytic activity to fuel cell oxygen reduction, and therefore it is desirable and the most practical fuel-cell catalyst always.But the price of its costliness and limited resources seriously constrain the sizable application of commercializing fuel cells.At present, mainly contain two kinds of methods in order to reduce platinum (Pt) catalyst price: one is the carrying capacity reducing platinum (Pt) catalyst, in commercialization process in a short time, catalyst containing the platinum (Pt) of low dosage is optimal selection, but, because the reserves of platinum (Pt) are not enough, consider from long term growth, development of new non-precious metal catalyst is only the real fuel cell that solves and realizes business-like most fundamental way [Science323,760 (2009) early; NatNanotechnol7,394 (2012)].
Since Jasinski in 1964 finds that cobalt phthalocyanine has certain oxygen reduction catalytic activity at alkaline medium, metal-nitrogen Conjugate macrocycle compound starts as oxygen cathode non-precious metal catalyst receive much concern [Nature201,1212 (1964); Electrochim.Acta55,2853 (2010)].But in acid medium, carbon-carried transition metal macrocyclic compound is unstable easily to be decomposed, and makes its catalytic activity greatly reduce.Research afterwards finds that heat treatment process (~ 400 DEG C-1000 DEG C) is incorporated into catalyst synthesis processes can make the stability of catalyst and activity be greatly improved, and the catalyst structure formed after treatment of different temperature is different, thus has caused the thinking to oxygen reduction catalytic activity position.Dodelet etc. think that the activated centre of oxygen reduction reaction is the M-Nx-C structure [Science324,71 (2009)] be made up of central metal, nitrogen and carbon matrix.The graphite nitrogen of carbon matrix surface doping and pyridine nitrogen play an important role to oxygen reduction reaction separately to have researcher to think, and in pyrolytic process, central metal facilitates the combination of nitrogen and carbon, therefore after heat treatment, catalyst activity is greatly improved [JCatal.239,83 (2006); J.Phys.Chem.C113,6730 (2009)].In recent years, studies have found that the existence of sulphur also has certain facilitation [AppliedCatalysisB:Environmental125,197 (2012)] to oxygen reduction activity.
Carbon carries nitrogen containing transition metal macrocyclic compound after heat treatment, and its oxygen reduction activity and stability all carry platinum (Pt) catalyst close to commercialization carbon, is therefore considered to the oxygen reduction catalyst of most potential replacement platinum (Pt).But its structure and catalytic mechanism are also completely not clear and definite, and active also have a certain distance with stability compared with platinum (Pt), can't meet the requirement of fuel cell industrialization at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of non-precious metal catalyst and the Synthesis and applications thereof with higher catalytic activity.
In order to solve the problems of the technologies described above, the invention provides a kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, it is characterized in that, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises material with carbon element 30wt%-90wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 10wt%-70wt%.
Preferably, described catalyst precursor also comprises the second active component 0wt%-60wt%.
More preferably, the second described active component comprises active metal source and activated nitrogen source, and described active metal source is at least one in Schweinfurt green, ferric acetate, cobalt acetate, nickel acetate, acetic acid molybdenum, manganese acetate, vanadium acetylacetonate, acetyl acetone vanadium, vanadyl acetylacetonate, acetylacetone,2,4-pentanedione platinum and palladium acetylacetonate; Described activated nitrogen source is pyridine, first class pyridine, pyridine carboxylic acid, pyrroles, ethylenediamine, DMF, DMA, 3, and at least one in 3 '-dihydroxy diphenylamine and 1-METHYLPYRROLIDONE.
Preferably, described material with carbon element is active carbon VlucanXC-72R, BP2000, CNT, carbon nano-fiber, nano cages, Graphene or graphene oxide.
Present invention also offers the preparation method of above-mentioned carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, it is characterized in that, concrete steps comprise:
The first step: material with carbon element 30wt%-90wt% (with the gross weight of catalyst precursor for benchmark) and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 10wt%-70wt% (with the gross weight of catalyst precursor for benchmark) are dissolved in solvent, be ground to solvent volatilization completely, drying, obtains catalyst precursor;
Second step: the catalyst precursor of first step gained is warming up to 600 ~ 1100 DEG C of roasting reduction process 2 ~ 4h with 5 ~ 25 DEG C/min under inert gas atmosphere protection, obtains carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst.
Preferably, the second active component 0wt%-60wt% is also dissolved with in the solvent in the described first step.(with the gross weight of catalyst precursor for benchmark)
Preferably, the solvent in the described first step is deionized water, methyl alcohol, ethanol, acetone, chloroform or oxolane.
Preferably, the inert gas in described second step is nitrogen or argon gas.
Present invention also offers a kind of method preparing membrane-membrane electrode for fuel cell combination, it is characterized in that, adopt above-mentioned carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, concrete steps are: be distributed in aqueous isopropanol by above-mentioned carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, obtain catalyst solution after ultrasonic; Described catalyst solution is transferred on GC (glass carbon) electrode, methanol solution and Nafion solution are mixed as binding agent, binding agent is dropped in the catalyst solution transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
Preferably, direct alkaline fuel cell, alkaline polymer fuel cell, metal-air battery or microbiological fuel cell that described fuel cell is is liquid fuel with methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether.
Preferably, the mass ratio of the weight percent concentration of described methanol solution to be 99.5wt%-99.9wt%, Nafion solution quality percent concentration be 5wt%, Nafion solution and methanol solution is 1:5
-1:70.
Preferably, the load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 40 μ g/cm
2-800 μ g/cm
2.
In described tetrasulfonic acid base copper phthalocyanine tetrasodium salt (CuTSPc), existing N element has again S element.
Compared with prior art, the invention has the beneficial effects as follows:
(1) the present invention is non-precious metal catalyst, by high temperature pyrolysis process, at alkaline medium System forming, there is the pyridine nitrogen of high N-and S-content and graphite nitrogen (Nx-C) composite construction and C-Sn-C structure, significantly improve the catalytic activity to oxygen;
(2) with the addition of the second active component in catalyst precursor of the present invention, namely organic metal salt dopping and N doping are carried out to carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, add catalytic activity.
(3) preparation method of the present invention is simple, easy operation, cost are low, greatly reduce the dependence to precious metals pt, make it have a good application prospect in fields such as direct alkaline fuel cell, alkaline polymer fuel cell, metal-air battery or microbiological fuel cells.
Accompanying drawing explanation
Fig. 1 is the mass fraction of tetrasulfonic acid base copper phthalocyanine tetrasodium salt at different heat treatment temperature is that the CuTSPc/C of 30% is at O
2polarization curve in saturated 0.1MKOH; (wherein: CuTsPc/C-non corresponding embodiment 5, CuTsPc/C
-the corresponding embodiment 7 of 600 corresponding embodiments 6, CuTsPc/C-700, the corresponding embodiment 8 of CuTsPc/C-800)
Fig. 2 is that the mass fraction of the tetrasulfonic acid base copper phthalocyanine tetrasodium salt of different carrying capacity is 30% and heats to the CuTSPc/C after 700 ° 0
2polarization curve in saturated 0.1MKOH; (wherein: 40 μ gcm
-2corresponding embodiment 9,80.8 μ gcm
-2corresponding embodiment 10,202 μ gcm
-2corresponding embodiment 11,505 μ gcm
-2corresponding embodiment 12,808 μ gcm
-2corresponding embodiment 13)
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
Take 0.060g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.140gVulcanXC-72R carbon dust is placed in agate mortar.Divide afterwards and add 3ml, 4ml, 3ml for three times respectively and analyze pure methyl alcohol, be all fully ground to methyl alcohol volatilization for three times completely.Agate mortar and mixture that the inside fills are put into vacuum drying 1h at vacuum drying oven 40 DEG C, obtain the presoma (CuTSPc/C-non catalyst) of required CuTSPc/C catalyst.
Embodiment 2
A kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises VulcanXC-72R carbon dust 30wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 70wt%.Its preparation method is: take 0.060g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.140gVulcanXC-72R carbon dust is placed in agate mortar.Divide afterwards and add 3ml, 4ml, 3ml for three times respectively and analyze pure methyl alcohol, be all fully ground to methyl alcohol volatilization for three times completely.Agate mortar and mixture that the inside fills are put into vacuum drying 1h at vacuum drying oven 40 DEG C, obtain the presoma of required CuTSPc/C catalyst.Dried mixture is placed in quartz boat, at N
2be increased to roasting reduction process 2h under 600 DEG C of conditions with 20 DEG C/min heating rate under atmosphere protection, obtain carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst (CuTSPc/C-600 catalyst).
Embodiment 3
A kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises VulcanXC-72R carbon dust 30wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 70wt%.Its preparation method is: take 0.060g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.140gVulcanXC-72R carbon dust is placed in agate mortar.Divide afterwards and add 3ml, 4ml, 3ml for three times respectively and analyze pure methyl alcohol, be all fully ground to methyl alcohol volatilization for three times completely.Agate mortar and mixture that the inside fills are put into vacuum drying 1h at vacuum drying oven 40 DEG C, obtain the presoma of required CuTSPc/C catalyst.Dried mixture is placed in quartz boat; under N2 atmosphere protection, be increased to roasting reduction process 2h under 700 DEG C of conditions with 20 DEG C/min heating rate, obtain carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst (CuTSPc/C-700 catalyst).
Embodiment 4
A kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises VulcanXC-72R carbon dust 30wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 70wt%.Its preparation method is: take 0.060g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.140gVulcanXC-72R carbon dust is placed in agate mortar.Divide afterwards and add 3ml, 4ml, 3ml for three times respectively and analyze pure methyl alcohol, be all fully ground to methyl alcohol volatilization for three times completely.Agate mortar and mixture that the inside fills are put into vacuum drying 1h at vacuum drying oven 40 DEG C, obtain the presoma of required CuTSPc/C catalyst.Dried mixture is placed in quartz boat, at N
2be increased to roasting reduction process 2h under 800 DEG C of conditions with 20 DEG C/min heating rate under atmosphere protection, obtain carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst (CuTSPc/C-800 catalyst).
Embodiment 5
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 1 of 4mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on catalyst that oneself transfers on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst (CuTSPc/C-non) in described membrane-membrane electrode for fuel cell combination is 80.8 μ g/cm
2.
Embodiment 6
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 2 of 4mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst (CuTSPc/C-600) in described membrane-membrane electrode for fuel cell combination is 80.8 μ g/cm
2.
Embodiment 7
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 4mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst (CuTSPc/C-700) in described membrane-membrane electrode for fuel cell combination is 80.8 μ g/cm
2.
Embodiment 8
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 4 of 4mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst (CuTSPc/C-800) in described membrane-membrane electrode for fuel cell combination is 80.S μ g/cm
2.
Embodiment 9
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 2mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 40.4 μ g/cm
2.
Embodiment 10
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 4mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to a diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 80.8 μ g/cm
2.
Embodiment 11
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 10mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on catalyst that oneself transfers on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 202 μ g/cm
2.
Embodiment 12
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 25mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 505 μ g/cm
2.
Embodiment 13
A kind of method preparing membrane-membrane electrode for fuel cell combination, concrete steps for: the concentration carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst described in the embodiment 3 of 40mg being distributed to 2ml is in the aqueous isopropanol of 99.7%, under ultrasonication, obtain catalyst solution.Pipetting the above-mentioned catalyst solution of 10 μ l with micropipette rifle, to transfer to diameter be 0.2475cm
2gC electrode on.Using concentration be 99.5% methanol solution and mass percent concentration be 5wt% Nafion solution in mass ratio for 1:50 mixing as binding agent, binding agent is dropped on the catalyst transferred on glass carbon (GC) electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.The load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 808 μ g/cm
2.
Embodiment 14
A kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises carbon black BP200010wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 90wt%.Its preparation method is: take 0.010g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.090g carbon black BP2000 is placed in agate mortar.Add 8ml afterwards and analyze pure chloroform, be fully ground to volatilization completely.Agate mortar and mixture that the inside fills are put into vacuum drying 1h at vacuum drying oven 40 DEG C, obtain required CuTSPc/C catalyst precursor.Dried mixture is placed in quartz boat, at N
2be increased to roasting reduction process 2h under 700 DEG C of conditions with 20 DEG C/min heating rate under atmosphere protection, obtain carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst (10%CuTSPc/BP-700 catalyst).
Embodiment 15
A kind of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises VulcanXC-72R carbon dust 60wt%, tetrasulfonic acid base copper phthalocyanine tetrasodium salt 35wt% and Schweinfurt green 15.7wt% (wherein in Schweinfurt green, the content of copper accounts for 5wt%).Its preparation method is: take 0.0157g Schweinfurt green, and 0.035g tetrasulfonic acid base copper phthalocyanine tetrasodium salt and 0.060gVulcanXC-72R carbon dust are placed in agate mortar, adds 10ml and analyzes pure methyl alcohol, is fully ground to methyl alcohol volatilization completely.Agate mortar and mixture are put into vacuum drying 1h at vacuum drying oven 40 DEG C, afterwards, dried mixture is placed in quartz boat, at N
2be increased to roasting reduction process 2h under 700 DEG C of conditions with 20 DEG C/min heating rate under atmosphere protection, obtain carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst (35%CuTSPc-5%Cu/C-700 catalyst).
Membrane-membrane electrode for fuel cell combination in embodiment 5-13 is carried out electrochemical property test as follows:
The electrochemical property test of CuTSPc/C catalyst uses Rotation ring disk electrode technology (RDE) to carry out in traditional three-electrode system.Electrolyte is 0.1MKOH, and working electrode is glass carbon (GC) electrode of loaded Cu TSPc/C catalyst, and reference electrode is saturated calomel electrode, is Pt silk electrode to electrode.
Can find from figure l and Fig. 2, the CuTSPc/C catalyst prepared in the present invention has higher activity and stability.30%CuTSPc/C composite catalyst prepared at 700 DEG C shows best catalytic activity.The gas-diffusion electrode prepared with it is at 0.1MKOH electrolyte solution and saturated 0
2under atmosphere, 0.11V (relative to standard hydrogen electrode) can produce obvious hydrogen reduction electric current, and half wave potential is at-0.02V, and greatest limit diffusion current density is 3.78mAcm
-2.In addition, when CuTSPc/C carrying capacity is at 505 μ g/cm
2time, can produce obvious hydrogen reduction electric current at 0.16V (relative to standard hydrogen electrode), half wave potential is 0.03V, and shuffled nearly 50mV, and greatest limit dissufion current increases 96%.
Claims (7)
1. a carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst, it is characterized in that, be made up through roasting reduction process of catalyst precursor, described catalyst precursor comprises material with carbon element 30wt%-90wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 10wt%-70wt%; Described catalyst precursor also comprises the second active component 0wt%-60wt%, do not comprise 0wt%, the second described active component comprises active metal source and activated nitrogen source, and described active metal source is at least one in Schweinfurt green, ferric acetate, cobalt acetate, nickel acetate, acetic acid molybdenum, manganese acetate, acetyl acetone vanadium, acetylacetone,2,4-pentanedione platinum and palladium acetylacetonate; Described activated nitrogen source is pyridine, picoline, pyridine carboxylic acid, pyrroles, ethylenediamine, DMF, DMA, 3, and at least one in 3 '-dihydroxy diphenylamine and 1-METHYLPYRROLIDONE.
2. carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst as claimed in claim 1, it is characterized in that, described material with carbon element is active carbon VlucanXC-72R, BP2000, CNT, carbon nano-fiber, nano cages or Graphene.
3. the preparation method of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst according to any one of claim 1-2, it is characterized in that, concrete steps comprise:
The first step: material with carbon element 30wt%-90wt% and tetrasulfonic acid base copper phthalocyanine tetrasodium salt 10wt%-70wt% is dissolved in solvent, also be dissolved with the second active component 0wt%-60wt% in described solvent, do not comprise 0wt%, be ground to solvent volatilization completely, drying, obtains catalyst precursor;
Second step: by the catalyst precursor of first step gained inert gas atmosphere protection under with 5 ~ 25
oc/min is warming up to 600 ~ 1100
oc roasting reduction process 2 ~ 4h, obtains carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel cell composite catalyst.
4. the preparation method of carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst as claimed in claim 3, it is characterized in that, the solvent in the described first step is deionized water, methyl alcohol, ethanol, acetone, chloroform or oxolane.
5. prepare the method for membrane-membrane electrode for fuel cell combination for one kind, it is characterized in that, adopt the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst according to any one of claim 1-2, concrete steps for: the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst according to any one of claim 1-2 is distributed in aqueous isopropanol, after ultrasonic, obtains catalyst solution; Described catalyst solution is transferred on GC electrode, methanol solution and Nafion solution are mixed as binding agent, binding agent is dropped in the catalyst solution transferred on glass-carbon electrode, naturally dry, obtain membrane-membrane electrode for fuel cell combination.
6. prepare the method for membrane-membrane electrode for fuel cell combination as claimed in claim 5, it is characterized in that, direct alkaline fuel cell, alkaline polymer fuel cell, metal-air battery or microbiological fuel cell that described fuel cell is is liquid fuel with methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether.
7. prepare the method for membrane-membrane electrode for fuel cell combination as claimed in claim 5, it is characterized in that, the load capacity of the carbon load tetrasulfonic acid base copper phthalocyanine tetrasodium salt fuel-cell catalyst in described membrane-membrane electrode for fuel cell combination is 40 μ g/cm
2-800 μ g/cm
2.
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| JP6672935B2 (en) * | 2015-03-30 | 2020-03-25 | 東洋インキＳｃホールディングス株式会社 | Carbon catalyst, method for producing the same, catalyst ink, and fuel cell |
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| US4828941A (en) * | 1986-06-04 | 1989-05-09 | Basf Aktiengesellschaft | Methanol/air fuel cells |
| CN102489328A (en) * | 2011-12-02 | 2012-06-13 | 东华大学 | Carbon-loaded pyridine-nitrogen-modified cobalt-phthalocyanine catalyst, and preparation method and application thereof |
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
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2013
- 2013-10-30 CN CN201310530979.9A patent/CN103586063B/en not_active Expired - Fee Related
Patent Citations (3)
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| US4828941A (en) * | 1986-06-04 | 1989-05-09 | Basf Aktiengesellschaft | Methanol/air fuel cells |
| CN102489328A (en) * | 2011-12-02 | 2012-06-13 | 东华大学 | Carbon-loaded pyridine-nitrogen-modified cobalt-phthalocyanine catalyst, and preparation method and application thereof |
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
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| "Novel methanol electro-oxidation catalyst assisting with functional phthalocyanine supports";Wu Jingjie，et al;《Electrochimica Acta》;20080926;第54卷;第2.1-2.2节，第4节 * |
| "碳载钴酞菁的吡啶氮修饰化及其在碱性介质中的高活性电催化性能";戴先逢，等;《中国科技论文在线》;20120531;第2页第3段，第3页第1段，第1.2节，第2.1节，图1 * |
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| CN103586063A (en) | 2014-02-19 |
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