CN104900893A - Method and device for optical driving rapid preparation of membrane electrode and application of membrane electrode - Google Patents
Method and device for optical driving rapid preparation of membrane electrode and application of membrane electrode Download PDFInfo
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- CN104900893A CN104900893A CN201410084350.0A CN201410084350A CN104900893A CN 104900893 A CN104900893 A CN 104900893A CN 201410084350 A CN201410084350 A CN 201410084350A CN 104900893 A CN104900893 A CN 104900893A
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- 239000012528 membrane Substances 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003287 optical effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 105
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 4
- 150000002678 macrocyclic compounds Chemical class 0.000 claims abstract description 3
- -1 transition metal macrocycle Chemical class 0.000 claims description 42
- 238000007789 sealing Methods 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 19
- 229910052723 transition metal Inorganic materials 0.000 claims description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 18
- 229960005070 ascorbic acid Drugs 0.000 claims description 18
- 235000010323 ascorbic acid Nutrition 0.000 claims description 18
- 239000011668 ascorbic acid Substances 0.000 claims description 18
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 7
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 claims description 7
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003011 anion exchange membrane Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 4
- NJSORKGSYPMGEJ-UHFFFAOYSA-N [Zn+2].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn+2].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NJSORKGSYPMGEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006393 polyether sulfone Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229950003776 protoporphyrin Drugs 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 description 54
- 239000003054 catalyst Substances 0.000 description 53
- 239000007864 aqueous solution Substances 0.000 description 40
- 229920000557 Nafion® Polymers 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000000376 reactant Substances 0.000 description 18
- 229910002027 silica gel Inorganic materials 0.000 description 18
- 239000000741 silica gel Substances 0.000 description 18
- 229960001866 silicon dioxide Drugs 0.000 description 18
- 238000011010 flushing procedure Methods 0.000 description 15
- 229910052736 halogen Inorganic materials 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 239000010937 tungsten Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000001476 alcoholic effect Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 5
- 229910052622 kaolinite Inorganic materials 0.000 description 5
- 238000007654 immersion Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010023 transfer printing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a method and device for optical driving rapid preparation of a membrane electrode and an application of the membrane electrode; a polymer electrolyte membrane loaded with a metal macrocyclic compound is placed in a reaction device, a mixed solution of a platinum metal precursor and a reducing agent is added into a reaction tank, platinum rapidly nucleates and grows on the polymer electrolyte membrane under an illumination condition, and thus the membrane electrode is obtained. The method is simple in process, can rapidly prepare the membrane electrode, and is good in repeatability and prone to mass production of the membrane electrode.
Description
Technical field
The invention belongs to electrochemical field (membrane electrode technology of preparing), be specifically related to a kind of optical drive and prepare the method for membrane electrode, device and application fast.
Background technology
Membrane electrode system (being made up of polymer dielectric film and catalyst layer) is core and the key element of hydrogen/oxygen Proton Exchange Membrane Fuel Cells, the directly device such as alcohol fuel battery and SPE water electrolysis, and its performance directly affects the performance of fuel cell and electrolytic water device.The preparation method optimizing membrane electrode improves an important method of its performance.So far, people have carried out extensive research to the preparation technology of membrane electrode and have proposed multiple method.There is carrier-free can be divided into two kinds of patterns according to catalyst.The first is the preparation of supported catalyst layer, platinum to be supported on a catalyst support Kaolinite Preparation of Catalyst layer again.Such as: spraying process-at 100-150 DEG C, Pt/C catalyst pulp is sprayed on (CN200810024885.3) in proton exchange membrane; Silk screen print method-use catalyst pulp is by catalyst wire reticulated printing Kaolinite Preparation of Catalyst layer (CN200710130584.4) in proton exchange membrane; Turn platen press-by Pt/C catalyst pulp to be first coated in and to turn on press mold, solvent evaporates, by hot-pressing transfer printing to (CN101355166A, CN101752570A) in proton exchange membrane; Or ground floor catalyst is sprayed on substrate, catalyst layer sprays proton exchange resins and forms proton exchange membrane layer, then spray second layer catalyst layer.In spraying process or silk screen print method, the solvent of catalyst pulp contains organic solvent as ethanol, isopropyl alcohol, propyl alcohol etc., and proton exchange membrane runs into the easy swelling set of organic solvent, causes the easy skewness of catalyst.Because before transfer printing, solvent is volatilized removing, transfer printing overcomes the problem of proton exchange membrane swelling set, but catalyst is easy to cohere with offset medium.Sum up supported catalyst layer preparation method, these methods first need configure catalyst pulp, then Kaolinite Preparation of Catalyst layer on the polymer electrolyte membrane, and technique is more loaded down with trivial details, and each step all exists the problem of catalyst waste.In addition, in order to improve the combination of catalyst and polymer dielectric film, proton membrane exchanger resin is often added in catalyst pulp, but proton exchange resins is easy to wrap up catalyst, causes Pt to lack three phase boundary, there is lower utilance, as in G.Sasikumar report, regulate the addition of proton exchange film resin with optimum, the utilance of Pt is the highest only has about 50% (Journal of Power Sources, 2004).
Second method is the preparation without supported catalyst layer, is directly prepared on the polymer electrolyte membrane by catalyst, is that a step prepares film-electrode method, greatly reduce the problem of catalyst waste, catalyst layer is combined comparatively tight with film, and is easy to build three phase boundary, improves the utilance of Pt.Such as: immersion reduction method-by Nanfion film immersion is at Pt (NH
3)
4cl
2in solution, Pt (NH
3)
4 2+with the H in film
+exchange, and then by film immersion at NaBH
4in, Pt is reduced, obtains membrane electrode (B.-J.Hwang, Mat.Electrochem.Systems, 2001), Catalytic Layer prepared by immersion reduction method is combined with film firmly, even compact, but the carrying capacity of Pt is wayward, prepare that required time is longer is not easy to volume production membrane electrode; Vacuum sputtering-using Pt as negative electrode, with Nafion film for anode, apply high voltage, Pt is splashed on Nafion film and forms catalyst layer, obtains membrane electrode (Masaaki Katoh, J.Photoploymer Science and Technology, 2003), vacuum sputtering prepares the thickness that membrane electrode can reduce catalyst layer, reduces the consumption of Pt, but complex process, expensive, improve the preparation cost of membrane electrode.
In order to improve the utilization ratio of Pt, simply, Kaolinite Preparation of Catalyst carrying capacity is controlled rapidly membrane electrode, the invention discloses a kind of optical drive and prepare the method for membrane electrode, device and application fast.
Summary of the invention
The object of the invention is to improve the utilization ratio of Pt, and simply, Kaolinite Preparation of Catalyst carrying capacity is controlled fast membrane electrode.
In order to realize this object, technical scheme of the present invention is: the polymer dielectric film being supported with transition metal macrocycle is placed in reaction unit, add the mixed solution of platinum presoma and reducing agent, under illumination condition, platinum fast nucleation growth on the polymer electrolyte membrane, obtains membrane electrode;
Platinum presoma is one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite, and concentration range is 0.1-100mM;
Reducing agent is the mixture of one or two or more kinds in hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid, and concentration range is 10-1000mM;
Light source is one or more in laser, visible ray and ultraviolet light;
Intensity of illumination scope is 0.1-10
6nmol cm
-2s
-1;
Light application time scope is 1-1800s.
Optical drive provided by the present invention prepares the method for membrane electrode fast, and described transition metal macrocycle is the p-sulfonic group phenyl of 4() zinc (II) porphyrin, 4(N-picoline) one or more mixture in zinc (II) porphyrin, zinc (II) protoporphyrin, octaethyl zinc (II) porphyrin, tetraphenyl zinc (II) porphyrin, germanium phthalocyanine and magnesium phthalocyanine.
Optical drive provided by the present invention prepares the method for membrane electrode fast, and described polymer dielectric film is anion-exchange membrane or cation-exchange membrane;
The fixed group of anion-exchange membrane is that primary amino radical, secondary amino group, uncle are amino, one or more mixture in season amino, fragrant amino, and macromolecular scaffold is one or more the blend in the copolymer of the copolymer of the copolymer of styrene and divinylbenzene, polysulfones, polyvinylidene fluoride, polyethylene benzyl chloride, anion exchange resin, polyether sulfone, divinylbenzene and dimethylamino-propyl-MAAm, methyl methacrylate and glycidyl methacrylate;
The fixed group of cation-exchange membrane is sulfonic group (-SO
3or phosphate (-PO H)
3h
2) in one or both mixing, macromolecular scaffold is one or more the blend in the copolymer of styrene and divinylbenzene, butadiene and cinnamic copolymer, polytetrafluoroethylene, polyphenylene oxide, polystyrene, polyether sulfone, polysulfones, polyether-ether-ketone.
Optical drive provided by the present invention prepares the method for membrane electrode fast, and the method for described carrying metal macrocyclic compound on polymer dielectric film comprises spraying, dipping or printing.
Optical drive provided by the present invention prepares the reaction unit of membrane electrode fast, described reaction unit is made up of printing opacity reaction vessel, sealing gasket 2 and the screw 5 that two structures are identical, wherein reaction vessel is made up of housing 1, reaction tank 3 and reinforced road 4, the side of housing 1 is provided with reinforced road 4, reinforced road 4 has reaction tank 3, the opening of reaction tank 3 is in the side of housing 1, and the mixed solution 8 of platinum presoma and reducing agent injects reaction tank 3 by reinforced road 4 and reacts; Reaction tank 3 is provided with sealing gasket 2, to prevent leak of liquid in the opening surrounding of housing 1 side; The side of housing 1 is also provided with screw hole 6; During use, by staggered relatively for the one side that two reaction vessels are provided with reaction tank 3 opening, the polymer dielectric film 7 being supported with transition metal macrocycle is inserted in the middle of two openings, and by screw hole 6, two reaction vessels are tightened together with screw 5.
Described reaction vessel is made up of light transmissive material or the light-proof material with optical transmission window;
The light transmittance of described light transmissive material or optical transmission window is 10%-100%.
The membrane electrode that optical drive is prepared fast, this membrane electrode is prepared by the method described in right 1, and this membrane electrode can be applicable in membrane cell and apparatus for electrolyzing.
Membrane electrode prepared by the method adopting optical drive of the present invention to prepare membrane electrode fast can be applied in fuel cell and electrolytic water device.
This technology compared with prior art, has following beneficial effect:
(1) apparatus structure is simple, can prepare membrane electrode fast, reproducible, is easy to volume production membrane electrode;
(2) can on dielectric film, make platinum utilization close to 100% the platinum presoma added located growth under illumination condition;
(3) can the carrying capacity of modulation polymer dielectric film both sides transition metal macrocycle, the concentration of Pt metal precursor or light application time etc. be passed through, control the carrying capacity of polymer dielectric film both sides Pt.
Accompanying drawing explanation
Fig. 1 is the structural representation that optical drive of the present invention prepares the reaction unit of membrane electrode fast, and wherein, 1-housing, 2-sealing gasket, 3-reaction tank, 4-feeds in raw material, 5-screw.
Fig. 2 is the structural representation that optical drive of the present invention prepares a reaction vessel in membrane electrode reaction unit fast, and wherein, 3-reaction tank, 4-feeds in raw material, 6-screw hole.
Fig. 3 is the structural representation that optical drive of the present invention prepares membrane electrode fast, and wherein, 1-housing, 2-sealing gasket, 3-reaction tank, 4-feeds in raw material, 5-screw, and 7-is supported with the polymer dielectric film of transition metal macrocycle, 8-reactant liquor.
Fig. 4 prepares the photo of the reaction unit of membrane electrode fast for the optical drive used in embodiments of the invention.
Fig. 5 is the molecular structural formula of octaethyl zinc protoporphyrin in the present invention.
Fig. 6 is the photo of the scanning electron microscopy (SEM) of embodiments of the invention 1 gained membrane electrode.
Fig. 7 is the photo of the scanning electron microscopy (SEM) of embodiments of the invention 1 gained membrane electrode.
Fig. 8 obtains by embodiments of the invention 2 photo of membrane electrode.
Fig. 9 is 4(N-picoline in the present invention) molecular structural formula of zinc protoporphyrin.
Figure 10 is the molecular structural formula of germanium phthalocyanine in the present invention.
Figure 11 supports 4(N-picoline in embodiments of the invention 5) UV-Vis spectra of the Nafion film of zinc protoporphyrin.
Figure 12 is the UV-Vis spectra of the Nafion film supporting octaethyl zinc protoporphyrin in embodiments of the invention 6.
Figure 13 is the molecular structural formula of magnesium phthalocyanine in the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is further described, but not thereby limiting the invention.
As shown in figures 1-4, the optical drive that the embodiment of the present invention adopts is prepared membrane electrode reaction unit fast and is made up of printing opacity reaction vessel, sealing gasket 2 and the screw 5 that two structures are identical, wherein reaction vessel is made up of housing 1, reaction tank 3 and reinforced road 4, the side of housing 1 is provided with reinforced road 4, reinforced road 4 has reaction tank 3, the opening of reaction tank 3 is in the side of housing 1, and the mixed solution 8 of platinum presoma and reducing agent injects reaction tank 3 by reinforced road 4 and reacts; Reaction tank 3 is provided with sealing gasket 2(the present embodiment in the opening surrounding of housing 1 side and adopts silicagel pad), to prevent leak of liquid; The side of housing 1 is also provided with screw hole 6; During use, by staggered relatively for the one side that two reaction vessels are provided with reaction tank 3 opening, the polymer dielectric film 7 being supported with transition metal macrocycle is inserted in the middle of two openings, and by screw hole 6, two reaction vessels are tightened together with screw 5.
Embodiment 1:
Get the Nafion115 film of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on the two reaction tank 3(reaction tanks 3 that silicagel pad (sealing gasket 2) seals is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mLK
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The molecular structural formula of octaethyl zinc protoporphyrin as shown in Figure 5.Fig. 6,7 is the SEM electromicroscopic photograph of the method gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film.
Embodiment 2:(changes light application time)
Get the Nafion117 film (belonging to cation-exchange membrane) of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), as shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By reaction system, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 3min, close light source, take out after 30min, obtain membrane electrode.
As shown in Figure 8, catalyst layer area is 2 × 2cm to gained membrane electrode.
Embodiment 3:(changes the kind of transition metal macrocycle)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 5min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, 4(N-picoline will be supported with) the Nafion film of the zinc protoporphyrin volume that is fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
4(N-picoline) zinc protoporphyrin molecular structural formula as shown in Figure 9.The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, spherical catalyst particles is evenly distributed on Nafion film, catalyst layer area is 2 × 2cm, the time of film blackening is different from the film required time that octaethyl zinc protoporphyrin supports, may because different from membrane interaction, soak same time, loading may be different, and photocatalysis effect is also different in addition.
Embodiment 4:(changes the kind of transition metal macrocycle)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 5min in germanium phthalocyanine alcoholic solution (100 μMs), the too much germanium phthalocyanine on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with germanium phthalocyanine being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmolcm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The molecular structural formula of germanium phthalocyanine as shown in Figure 10.The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, spherical catalyst particles is evenly distributed on Nafion film, catalyst layer area is 2 × 2cm, the time of film blackening is different from the film required time that octaethyl zinc protoporphyrin supports, may because different from membrane interaction, soak same time, loading may be different, and photocatalysis effect is also different.
Embodiment 5:(changes transition metal macrocycle loading on the polymer electrolyte membrane)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 10min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, 4(N-picoline will be supported with) the Nafion film of the zinc protoporphyrin volume that is fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
Supporting 4(N-picoline) UV-Vis spectra of the Nafion film of zinc protoporphyrin is as shown in figure 11.The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film, and catalyst layer area is 2 × 2cm.
Embodiment 6:(changes transition metal macrocycle loading on the polymer electrolyte membrane)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 10min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
Support the UV-Vis spectra of the Nafion film of octaethyl zinc protoporphyrin as shown in figure 12.The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film, and catalyst layer area is 2 × 2cm.
Embodiment 7:(changes the kind of polymer dielectric film)
Get the FAA-3-PK-130 film (belonging to anion-exchange membrane) of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume FAA-3-PK-130 film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL H
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The method acquired results is similar to embodiment 1,2 acquired results, obtain the catalyst layer of 2 × 2cm, and spherical catalyst particles is evenly distributed on Nafion film.
Embodiment 8:(changes transition metal macrocycle loading method)
Get the Nafion117 film of one 3.5 × 3.5cm, film is fixed on heating in vacuum platform, at 60 DEG C, use spray gun spraying octaethyl zinc protoporphyrin after ethanol volatilization completely, then spray another side, obtain the Nafion film that octaethyl zinc protoporphyrin supports.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(1.2mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmolcm
-2s
-1) irradiate 10min, close light source, allow Pt grow, obtain membrane electrode.
Embodiment 9:(changes the kind of Pt metal precursor)
Get the Nafion115 film of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL H
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The method acquired results is similar to embodiment 2 acquired results, and spherical catalyst particles is evenly distributed on Nafion film.
Embodiment 10:(reduces the concentration of Pt metal precursor)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 10min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, 4(N-picoline will be supported with) the Nafion film of the zinc protoporphyrin volume that is fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(1mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film, and catalyst layer area is 2 × 2cm.Because metal front bulk concentration reduces, reaction rate slows down, and time and the reaction required time of film blackening extend.
Embodiment 11:(increases the concentration of Pt metal precursor)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 10min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, 4(N-picoline will be supported with) the Nafion film of the zinc protoporphyrin volume that is fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(80mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film, and catalyst layer area is 2 × 2cm.Because metal front bulk concentration increases, reaction rate increases, and time and the reaction required time of film blackening shorten.
Embodiment 12:(changes the kind of reducing agent)
Get the Nafion115 film of one 3.5 × 3.5cm, be immersed in 10min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL citric acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
Embodiment 13:(reduces the concentration of reducing agent)
Get the Nafion115 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 10min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (80mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
The method gained membrane electrode is similar to embodiment 1,2 gained membrane electrode, and spherical catalyst particles is evenly distributed on Nafion film, and catalyst layer area is 2 × 2cm.Because the concentration of reducing agent reduces, reaction rate reduces, and the time of film blackening and reaction time extend.
Embodiment 14:(increases the concentration of reducing agent)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface, for subsequent use after 65 DEG C of dry 2h.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (280mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 5min, close light source, allow Pt grow, obtain membrane electrode.
Embodiment 15:(changes light source and light intensity)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 5min in octaethyl zinc protoporphyrin alcoholic solution (100 μMs), the too much octaethyl zinc protoporphyrin on flushing membrane surface, for subsequent use after 65 DEG C of dry 2h.As shown in Figures 1 to 3, at room temperature, the volume Nafion film being supported with octaethyl zinc protoporphyrin being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, at laser, (luminous intensity is 13.3 μMs of ol cm
-2s
-1) irradiate lower 40s, close light source, allow Pt grow, obtain membrane electrode.
Embodiment 16:(reduces the concentration of Pt metal precursor and reducing agent, increases light application time)
Get the Nafion117 film of one 3.5 × 3.5cm, be immersed in 4(N-picoline) the middle 10min of the zinc protoporphyrin aqueous solution (100 μMs), the too much 4(N-picoline on flushing membrane surface) zinc protoporphyrin.As shown in Figures 1 to 3, at room temperature, 4(N-picoline will be supported with) the Nafion film of the zinc protoporphyrin volume that is fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mL K
2ptCl
4(1.2mM) aqueous solution and 2mL ascorbic acid (20mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, under tungsten halogen lamp, (75V, luminous intensity is 570nmol cm
-2s
-1) irradiate 20min, close light source, allow Pt grow, obtain membrane electrode.
Embodiment 17:(changes the kind of polymer dielectric film and transition metal macrocycle, light source and light application time)
Get the FAP film (belonging to anion-exchange membrane) of one 3.5 × 3.5cm, be immersed in 5min in magnesium phthalocyanine alcoholic solution (100 μMs), the too much magnesium phthalocyanine on flushing membrane surface, for subsequent use after 65 DEG C of dry 2h.As shown in Figures 1 to 3, at room temperature, the volume FAP film being supported with magnesium phthalocyanine being fixed on two reaction tank 3(reaction tanks 3 of silicagel pad sealing is 2 × 2 × 0.3cm) between, tighten the screw 5.Get 2mLK
2ptCl
4(20mM) aqueous solution and 2mL ascorbic acid (150mM) aqueous solution are in a bottle, are added the reactant liquor of 1.2mL after mixing by reinforced road 4 in two reaction tanks 3 respectively.By device, at laser, (luminous intensity is 13.3 μMs of ol cm
-2s
-1) carry out 20s under irradiation, close light source, allow Pt grow, acquisition membrane electrode.
The molecular structural formula of magnesium phthalocyanine as shown in figure 13.
The invention is not restricted to above-mentioned illustrative example.The method that light source as described herein, intensity of illumination and time, the kind of transition metal macrocycle and the kind of loading, platinum presoma and reducing agent and concentration and transition metal macrocycle support, all have impact to the carrying capacity of catalyst, Average Particle Diameters and domain size distribution, influence each other between each factor, interrelated.When the timing of other conditions one, change a certain factor within the specific limits and can regulate and control the carrying capacity of catalyst, Average Particle Diameters and domain size distribution, exceed this scope and then no longer there is regulating and controlling effect, and need the mating reaction of other factors.Such as, the kind of light source, intensity of illumination and time, Pt metal precursor and reducing agent and concentration and transition metal macrocycle one timing, the loading of regulation and control transition metal macrocycle can change the carrying capacity of catalyst, average grain diameter and domain size distribution.
Claims (7)
1. an optical drive prepares the method for membrane electrode fast, it is characterized in that: the polymer dielectric film being supported with transition metal macrocycle is placed in reaction unit, add the mixed solution of platinum presoma and reducing agent, under illumination condition, platinum fast nucleation growth on the polymer electrolyte membrane, obtains membrane electrode;
Platinum presoma is one or two or more kinds in chloroplatinic acid, chloroplatinous acid, chloroplatinate, chloroplatinite, and concentration range is 0.1-100mM;
Reducing agent is the mixture of one or two or more kinds in hydrazine hydrate, ethanedioic acid, malic acid, citric acid, glucose, sucrose, ascorbic acid, and concentration range is 10-1000mM;
Light source is one or more in laser, visible ray and ultraviolet light;
Intensity of illumination scope is 0.1-10
6nmol cm
-2s
-1;
Light application time scope is 1-1800s.
2. prepare the method for membrane electrode according to optical drive according to claim 1 fast, it is characterized in that: described transition metal macrocycle is the p-sulfonic group phenyl of 4() zinc (II) porphyrin, 4(N-picoline) one or more mixture in zinc (II) porphyrin, zinc (II) protoporphyrin, octaethyl zinc (II) porphyrin, tetraphenyl zinc (II) porphyrin, germanium phthalocyanine and magnesium phthalocyanine.
3. prepare the method for membrane electrode according to optical drive according to claim 1 fast, it is characterized in that: described polymer dielectric film is anion-exchange membrane or cation-exchange membrane;
The fixed group of anion-exchange membrane is that primary amino radical, secondary amino group, uncle are amino, one or more mixture in season amino, fragrant amino, and macromolecular scaffold is one or more the blend in the copolymer of the copolymer of the copolymer of styrene and divinylbenzene, polysulfones, polyvinylidene fluoride, polyethylene benzyl chloride, anion exchange resin, polyether sulfone, divinylbenzene and dimethylamino-propyl-MAAm, methyl methacrylate and glycidyl methacrylate;
The fixed group of cation-exchange membrane is sulfonic group (-SO
3or phosphate (-PO H)
3h
2) in one or both mixing, macromolecular scaffold is one or more the blend in the copolymer of styrene and divinylbenzene, butadiene and cinnamic copolymer, polytetrafluoroethylene, polyphenylene oxide, polystyrene, polyether sulfone, polysulfones, polyether-ether-ketone.
4. prepare the method for membrane electrode according to optical drive according to claim 1 fast, it is characterized in that: the method for carrying metal macrocyclic compound on polymer dielectric film is spraying, floods or print process.
5. prepare the reaction unit of membrane electrode fast according to optical drive according to claim 1 for one kind, it is characterized in that: described reaction unit is by the identical printing opacity reaction vessel of two structures, sealing gasket (2) and screw (5) composition, wherein reaction vessel is by housing (1), reaction tank (3) and reinforced road (4) composition, the side of housing (1) is provided with reinforced road (4), reinforced road (4) has reaction tank (3), the opening of reaction tank (3) is in the side of housing (1), the mixed solution (8) of platinum presoma and reducing agent injects reaction tank (3) by reinforced road (4) and reacts, reaction tank (3) is provided with sealing gasket (2), to prevent leak of liquid in the opening surrounding of housing (1) side, the side of housing (1) is also provided with screw hole (6), during use, by staggered relatively for the one side that two reaction vessels are provided with reaction tank (3) opening, the polymer dielectric film (7) being supported with transition metal macrocycle is inserted in the middle of two openings, and by screw hole (6), two reaction vessels is tightened together with screw (5).
6. prepare the reaction unit of membrane electrode according to optical drive described in claim 5 fast, it is characterized in that: described reaction vessel is made up of light transmissive material or the light-proof material with optical transmission window, and the light transmittance of described light transmissive material or optical transmission window is 10%-100%.
7. the application of membrane electrode in fuel cell and electrolytic water device prepared of the method preparing membrane electrode fast according to optical drive described in claim 1.
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| CN113563350A (en) * | 2021-06-24 | 2021-10-29 | 浙江工业大学 | Compound with porphyrin structure and preparation method and application thereof |
| CN114865028A (en) * | 2022-05-05 | 2022-08-05 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
| CN115332590A (en) * | 2022-08-04 | 2022-11-11 | 大连理工大学 | Membrane electrode with hydrogen dissipation layer and preparation method and application thereof |
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| CN106856243A (en) * | 2017-01-10 | 2017-06-16 | 大连理工大学 | A kind of preparation method and application based on transition metal macrocycle ordering single electrode |
| CN106856243B (en) * | 2017-01-10 | 2020-04-07 | 大连理工大学 | Preparation method and application of ordered single electrode based on metal macrocyclic compound |
| CN113563350A (en) * | 2021-06-24 | 2021-10-29 | 浙江工业大学 | Compound with porphyrin structure and preparation method and application thereof |
| CN113563350B (en) * | 2021-06-24 | 2022-05-24 | 浙江工业大学 | Compound with porphyrin structure and preparation method and application thereof |
| CN114865028A (en) * | 2022-05-05 | 2022-08-05 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
| CN114865028B (en) * | 2022-05-05 | 2024-04-16 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
| CN115332590A (en) * | 2022-08-04 | 2022-11-11 | 大连理工大学 | Membrane electrode with hydrogen dissipation layer and preparation method and application thereof |
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