CN104307382A - Method for manufacturing hydrogen separating membrane - Google Patents
Method for manufacturing hydrogen separating membrane Download PDFInfo
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- CN104307382A CN104307382A CN201410612161.6A CN201410612161A CN104307382A CN 104307382 A CN104307382 A CN 104307382A CN 201410612161 A CN201410612161 A CN 201410612161A CN 104307382 A CN104307382 A CN 104307382A
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- catalytic metal
- ceramic material
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- hydrogen
- palladium
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 230000003197 catalytic effect Effects 0.000 claims abstract description 40
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 38
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims abstract description 9
- 229920000053 polysorbate 80 Polymers 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 238000007733 ion plating Methods 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims abstract description 6
- 229910003408 SrCeO3 Inorganic materials 0.000 claims abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 5
- 229910002761 BaCeO3 Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 17
- 239000011268 mixed slurry Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000010494 dissociation reaction Methods 0.000 abstract 3
- 230000005593 dissociations Effects 0.000 abstract 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000009257 reactivity Effects 0.000 abstract 2
- 238000004513 sizing Methods 0.000 abstract 2
- -1 and B Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- YMNMFUIJDSASQW-UHFFFAOYSA-N distrontium;oxygen(2-);vanadium Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[V].[V].[Sr+2].[Sr+2] YMNMFUIJDSASQW-UHFFFAOYSA-N 0.000 abstract 1
- 239000011812 mixed powder Substances 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007772 electroless plating Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a method for manufacturing a hydrogen separating membrane. The method comprises the following steps: A, mixing a nano-palladium powder and a gamma-aluminum oxide powder, and feeding a proper amount of water and surfactant Tween 80 into the mixed powder, so as to prepare a nano-palladium and gamma-aluminum oxide mixed sizing agent, and B, coating the mixed sizing agent prepared in step A onto ceramic material which is selected from tungsten trioxide (WO3), molybdenum trioxide (MoO3), barium vanadate (BaCeO3) or strontium vanadate (SrCeO3) ceramic perovskite or ceramic pyrochlore, airing and laying the material into an inert atmosphere furnace, and calcining the material, so as to form a nano-palladium and aluminum oxide composite material hydrogen through layer with small bores formed in the surface of ceramic material, and finally adhering catalytic metal with hydrogen dissociation and combination reactivity on the other surface of the ceramic material at a particle state; the catalytic metal with hydrogen dissociation and combination reactivity is noble metal, such as palladium (Pd) or ruthenium (Ru); the hydrogen dissociation and combination catalytic metal is adhered through an ion plating or sputtering method, wherein the size of particle does not exceed 20nm.
Description
Technical field
The present invention relates to a kind of method manufacturing hydrogen separation membrane.
Background technology
Palladium film due to good and high temperature resistant etc. the feature of hydrogen permeability, except being used as Hydrogen Separation and purifier, also for dehydrogenation, hydrogenation reactor.At present, researcher has carried out large quantity research to palladium and palldium alloy hydrogen permeation membrane thereof and has achieved remarkable achievement, mainly concentrates on palladium film preparation and penetration testing.But the research of palladium film also faces some challenges, is mainly manifested in: 1. because palladium is worth expensive, constantly reduce film thickness under therefore how ensureing the good situation of film integrality, increase the permeation flux of film, reduce costs; 2. how to select suitable supporter and optimize palladium film preparation technique, operating process is simplified, and preparation time shortens; 3. how to improve the stability of film in high temperature and Thermal Cycling, increase the service life of film.
The preparation method of metal current palladium film mainly contains chemical vapour deposition technique, physical vaporous deposition, electroless plating method, galvanoplastic etc., each method has oneself pluses and minuses, wherein electroless plating method is current widely used method, but chemical plating preprocessing process is loaded down with trivial details, consuming time, the acid solution that first supporter is put into stannic chloride by it carries out sensitization, and then the acid solution putting into palladium bichloride activates, this process more than 6-10 time repeatedly, and introduce Impurity Sn in this process, be easy to destroy the integrality of film and reduce the adhesion of film and supporter, thus reduce the service life of film.Therefore, many scholars improve electroless plating method, mainly avoid introducing Impurity Sn in this step of pretreatment.
The conventional palladium film prepared by electroless plating method, first transition one deck small aperture ceramic film on macropore supporter, carry out the activation sensitization of 6-10 time repeatedly again, and then adopt electroless plating method to prepare palladium film, the advantage of the method is: small aperture ceramic film is easy to make film fine and close when very thin, reduces costs, increases flux, but so also easily cause film to come off from supporter, less stable.In addition, whole process activation activation process is loaded down with trivial details consuming time, and introduces tin, destroys the integrality of film under being easy to high temperature.
Hydrogen separation membrane described in known such as following Japanese Patent Publication 7-185277 publication has as what use in fuel cell etc. the hydrogen separation membrane being only separated hydrogen function from hydrogen-rich gas.For the hydrogen separation membrane described in the document, use hydrogen permeability metal level (vanadium (V)) as base material, and its coated on both sides have metal diffusion control layer.In addition, this metal diffusion control layer surface using membranaceous be coated with palladium (Pd) as activation and promote hydrogen dissociate and combine catalytic metal (hereinafter also referred to as hydrogenolysis from combination catalytic metal).
In above-mentioned hydrogen separation membrane, as hydrogenolysis from being expensive with the palladium in conjunction with catalytic metal, therefore need the use amount controlling palladium (Pd) as much as possible.
The problems referred to above are not only limited to palladium (Pd), and with hydrogenolysis from relevant with in conjunction with other metal used in catalytic metal.
Summary of the invention
Consider above problem, the object of this invention is to provide a kind of method manufacturing hydrogen separation membrane.For reaching this object, the present invention by the following technical solutions:
Manufacture a method for hydrogen separation membrane, this manufacture method comprises the following steps:
A, Technique of Nano Pd powder to be mixed with gama-alumina powder, add suitable quantity of water and surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, described ceramic material is selected from, the ceramic perovskite of tungstic acid (WO3), molybdenum trioxide (MoO3), barium cerate (BaCeO3) or strontium cerate (SrCeO3) type or ceramic pyrochlore; Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble metal from the catalytic metal with association reaction activity, as palladium (Pd) or ruthenium (Ru); Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating or sputtering method, and wherein the size of particle is no more than 20nm.
Relevant object at least partially, the present invention relates to a kind of hydrogen separation membrane with other to achieve these goals.This hydrogen separation membrane comprises: as the ceramic material of base material; The hydrogen permeation membrane that described ceramic material surfaces is formed; With by by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape that another is formed on the surface.
According to above-mentioned hydrogen separation membrane, catalytic metal with the attachment of particle shape, therefore with in the past with compared with the situation of membranaceous formation catalytic metal, the surface area of the active interface of catalytic metal can be increased.Therefore, such as, if the surface area of this active interface be set as with the identical size of the surface area of the active interface of the catalytic metal in the situation of membranaceous formation catalytic metal, with compared with the situation of membranaceous formation catalytic metal, the use amount of catalytic metal can be controlled better.
Relevant object at least partially, the present invention relates to a kind of fuel cell with other to achieve these goals.This fuel cell comprises: above-mentioned hydrogen separation membrane; With the dielectric substrate with proton-conducting formed on the surface of described hydrogen separation membrane.
According to above-mentioned fuel cell, owing to using the hydrogen separation membrane that can control above-mentioned catalytic metal use amount, the manufacturing cost of fuel cell therefore can be controlled.
Detailed description of the invention
Embodiment 1
A, Technique of Nano Pd powder 10g to be mixed with gama-alumina powder 10g, add 200ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from, tungstic acid (WO3) body material; Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is precious metal palladium (Pd) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating or sputtering method, and wherein the size of particle is no more than 10nm.
Embodiment 2
A, Technique of Nano Pd powder 10g to be mixed with gama-alumina powder 20g, add 200ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from, molybdenum trioxide (MoO3); Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble ruthenium (Ru) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating or sputtering method, and wherein the size of particle is no more than 20nm.
Embodiment 3
A, Technique of Nano Pd powder 20g to be mixed with gama-alumina powder 10g, add 300ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from, barium cerate (BaCeO3); Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble ruthenium (Ru) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating method, and wherein the size of particle is no more than 10nm.
Embodiment 4
A, Technique of Nano Pd powder 10g to be mixed with gama-alumina powder 10g, add 200ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from strontium cerate (SrCeO3); Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble metal (Pd) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by sputtering method, and wherein the size of particle is no more than 20nm.
Embodiment 5
A, Technique of Nano Pd powder 20g to be mixed with gama-alumina powder 5g, add 200ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from strontium cerate (SrCeO3); Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble ruthenium (Ru) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating method, and wherein the size of particle is no more than 20nm.
Embodiment 6
A, Technique of Nano Pd powder 20g to be mixed with gama-alumina powder 5g, add 200ml water and 0.2g surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, and described ceramic material is selected from molybdenum trioxide (MoO3); Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble metal (Pd) from the catalytic metal with association reaction activity; Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating, and wherein the size of particle is no more than 10nm.
Claims (1)
1. manufacture a method for hydrogen separation membrane, comprise the following steps:
A, Technique of Nano Pd powder to be mixed with gama-alumina powder, add suitable quantity of water and surface active agent tween 80, prepare Technique of Nano Pd and gama-alumina mixed slurry;
B, mixed slurry steps A prepared are coated on ceramic material, described ceramic material is selected from, the ceramic perovskite of tungstic acid (WO3), molybdenum trioxide (MoO3), barium cerate (BaCeO3) or strontium cerate (SrCeO3) type or ceramic pyrochlore; Through drying, then put into inert atmosphere stove and calcine, be formed in the Technique of Nano Pd with small-bore and alumina composite material hydrogen transmission layer that ceramic material surfaces is formed; Finally by have hydrogen dissociate and the catalytic metal of association reaction activity is attached to described ceramic material with particle shape another on the surface; Described hydrogenolysis is noble metal from the catalytic metal with association reaction activity, as palladium (Pd) or ruthenium (Ru); Described hydrogenolysis is adhered to from in conjunction with catalytic metal by ion plating or sputtering method, and wherein the size of particle is no more than 20nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410612161.6A CN104307382A (en) | 2014-11-04 | 2014-11-04 | Method for manufacturing hydrogen separating membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410612161.6A CN104307382A (en) | 2014-11-04 | 2014-11-04 | Method for manufacturing hydrogen separating membrane |
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| Publication Number | Publication Date |
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| CN104307382A true CN104307382A (en) | 2015-01-28 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413777A (en) * | 1965-06-22 | 1968-12-03 | Engelhard Min & Chem | Hydrogen diffusion and method for producing same |
| CN1640527A (en) * | 2004-01-13 | 2005-07-20 | 中南大学 | Preparation method of filter membrane of palladium-based alloy/aperture gradient titanium-aluminum intermetallic compound homogeneous support body for hydrogen separation |
| CN1753722A (en) * | 2003-02-24 | 2006-03-29 | 福田金属箔粉工业株式会社 | Hydrogen separation membrane and process for producing the same |
| CN1946633A (en) * | 2004-04-26 | 2007-04-11 | 丰田自动车株式会社 | Hydrogen separation membrane and fuel cell, and manufacturing method therefor |
| CN101039742A (en) * | 2004-09-15 | 2007-09-19 | 韩国能源技术研究院 | Preparation method of palladium alloy composite membrane for hydrogen separation |
| CN101439267A (en) * | 2008-12-09 | 2009-05-27 | 南京工业大学 | A kind of preparation method of hydrogen permeable palladium composite membrane |
-
2014
- 2014-11-04 CN CN201410612161.6A patent/CN104307382A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413777A (en) * | 1965-06-22 | 1968-12-03 | Engelhard Min & Chem | Hydrogen diffusion and method for producing same |
| CN1753722A (en) * | 2003-02-24 | 2006-03-29 | 福田金属箔粉工业株式会社 | Hydrogen separation membrane and process for producing the same |
| CN1640527A (en) * | 2004-01-13 | 2005-07-20 | 中南大学 | Preparation method of filter membrane of palladium-based alloy/aperture gradient titanium-aluminum intermetallic compound homogeneous support body for hydrogen separation |
| CN1946633A (en) * | 2004-04-26 | 2007-04-11 | 丰田自动车株式会社 | Hydrogen separation membrane and fuel cell, and manufacturing method therefor |
| CN101039742A (en) * | 2004-09-15 | 2007-09-19 | 韩国能源技术研究院 | Preparation method of palladium alloy composite membrane for hydrogen separation |
| CN101439267A (en) * | 2008-12-09 | 2009-05-27 | 南京工业大学 | A kind of preparation method of hydrogen permeable palladium composite membrane |
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Application publication date: 20150128 |