CN1874841A - 水电解用贵金属氧化物催化剂 - Google Patents
水电解用贵金属氧化物催化剂 Download PDFInfo
- Publication number
- CN1874841A CN1874841A CNA2004800323407A CN200480032340A CN1874841A CN 1874841 A CN1874841 A CN 1874841A CN A2004800323407 A CNA2004800323407 A CN A2004800323407A CN 200480032340 A CN200480032340 A CN 200480032340A CN 1874841 A CN1874841 A CN 1874841A
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- CN
- China
- Prior art keywords
- catalyst
- oxide
- inorganic oxide
- pem
- yttrium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 title description 12
- 150000004706 metal oxides Chemical class 0.000 title description 12
- 239000010970 precious metal Substances 0.000 title description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001172 regenerating effect Effects 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 239000012528 membrane Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract 2
- -1 A12O3 Chemical compound 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- 229910000457 iridium oxide Inorganic materials 0.000 abstract 1
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- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
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- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 201000000760 cerebral cavernous malformation Diseases 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012705 liquid precursor Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JVCTYROWTAWTRK-UHFFFAOYSA-M CC([O-])=O.[Ru+3] Chemical compound CC([O-])=O.[Ru+3] JVCTYROWTAWTRK-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- XHAHJAIALMLSLF-UHFFFAOYSA-N N(=O)[Ru].[N+](=O)(O)[O-] Chemical compound N(=O)[Ru].[N+](=O)(O)[O-] XHAHJAIALMLSLF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- MOHYGSBMXIJZBJ-UHFFFAOYSA-N [Ir+4] Chemical compound [Ir+4] MOHYGSBMXIJZBJ-UHFFFAOYSA-N 0.000 description 1
- GWZHWRVINLCSIC-UHFFFAOYSA-N [Ir].[N+](=O)(O)[O-] Chemical compound [Ir].[N+](=O)(O)[O-] GWZHWRVINLCSIC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F1/46104—Devices therefor; Their operating or servicing
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
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- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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- 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
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Abstract
本发明涉及在PEM水电解装置中用作阳极催化剂的含氧化铱的催化剂。所要求的复合催化剂材料包含氧化铱(IrO2)和任选的氧化钌(RuO2)以及高表面积无机氧化物(例如TiO2、Al2O3、ZrO2及其混合物)。无机氧化物的BET表面积为50-400m2/g,水溶解度小于0.15g/l,按催化剂的总重计,其数量小于20重量%。所要求的催化剂的特征在于,在水电解中氧过压低和寿命长。所述的催化剂用于PEM水电解装置的电极、催化剂涂覆的薄膜和薄膜-电极组合件以及用于再生式燃料电池(RFC)、传感器和其它电化学装置。
Description
发明领域
本发明涉及贵金属氧化物催化剂,特别是涉及用于水电解、再生式燃料电池(RFC)或各种电解应用中的制氧电极的氧化铱基的催化剂。此外,还公开了这些催化剂材料在用于水电解装置的电极、涂覆有催化剂的薄膜(CCMs)和薄膜-电极组合件(MEAs)中的应用。
发明背景
在未来基于可再生资源的能源体制中,氢将成为主要的能源载体。水的电解是用可再生资源生产氢的最实用的途径。电解装置的投资和生产费用决定了体系的总经济性,决定这一途径是否能成为氢生产的可行方法。用水电解生产氢的费用在很大程度上受电力消耗的影响,电力消耗可占氢总生产费用的约70%。
通常在现有技术中使用两种不同类型的水电解装置:碱性电解装置和PEM水电解装置。与传统的碱性电解装置相比,使用聚合物电解质薄膜(“PEM”)和贵金属氧化物催化剂的水电解装置能在相当高的电流密度和相当低的比能耗下操作,具有装置利用率高和生产费用低的优点。在最好的PEM电解装置中,在3A/cm2下已得到1.67V的电解池电压。这一电解池电压与最新的碱性电解装置相当,后者通常在0.2A/cm2下操作。这就意味着碱性电解装置在相同的电力消耗下生产相同数量的氢要比PEM电解装置需要15倍大的有效面积。
所以,本发明涉及用于PEM水电解装置的催化剂的改进。
原则上,PEM水电解装置的构造类似PEM燃料电池,但是它们以不同的方式操作。在PEM燃料电池操作过程中,在燃料电池的阴极上进行氧的还原,而在阳极上进行氢的氧化。总之,生成水并产生电流。在PEM水电解装置中,电流和电极是相反的,发生水的分解。在阳极上释放氧(简称“OER”=氧释放反应),而在阴极上发生质子(H+)的还原(简称“HER”=氢释放反应),其中所述质子穿过聚合物电解质薄膜迁移。因此,借助电流水分解成氢气和氧气。所述的反应可汇集成以下反应:
PEM水电解装置通常包含聚合物电解质薄膜(例如DuPont公司的Nafion®),它夹在一对电极层之间和分别安装在所述电极层两侧的一对多孔集流器(或气体扩散层)之间。
在PEM水电解装置中,铂/碳催化剂用作阳极电催化剂(用于氢的氧化)和阴极电催化剂(用于氧的还原)。在PEM水电解装置中,在阳极侧不能使用碳基材料例如铂/碳催化剂和碳纤维基的气体扩散层(GDLs),因为碳被水电解的过程中释放的氧腐蚀。
为了制造用于PEM电解装置的薄膜-电极组合件,制备了含有催化剂粉末、溶剂和任选的聚合物电解质(即“离聚物”)材料的催化剂涂料,然后直接涂覆到薄膜上,或涂覆到气体扩散层上然后再与薄膜接触。该组合件的制造类似于用于PEM燃料电池的薄膜-电极组合件(MEAs)的制造,其内容在文献(例如参见US 5861222、US 6309772和US 6500217)中广泛描述。
在所有的贵金属中,对于在阴极上氢的释放反应(HER)来说,铂是最有活性的催化剂,并可在中等负载量下应用。就氯和氧的释放过程来说,铱和氧化铱的独特电催化性质是大家熟悉的(参考DEGUSSA-Edelmetalltaschenbuch,Chapter 8.3.3,Huethig-Verlag,Heidelberg/Germany,1995)。因此,对于在阳极侧氧释放反应(OER)来说,铱无论纯金属形式或为氧化物都是优选的。但是,对于某些场合,可加入其它贵金属氧化物(优选钌或铂的氧化物)。
在PEM水电解装置中,负载在阳极和阴极上的贵金属催化剂仍是相当高的,例如3-5mg p.m./cm2或更大。所以,需要开发有较低氧过压和较长寿命的改进催化剂,它能减少电解装置的催化剂载量。
相关技术的描述
GB 1195871公开了热处理的RuO2和IrO2化合物及其混合物在活化的钛电极(所谓的“DSA”®=尺寸稳定阳极)中的应用。所述产品广泛用于在氯碱电解中生产氯。钌和铱的氧化物通过液体前体热分解法沉积在导电的金属钛基底上。
热处理沉积法不适用于薄膜为基础的PEM电解装置,因为聚合物电解质薄膜的热稳定性低。此外,液体前体会渗透薄膜并污染离聚物。此外,TiO2和各种其它无机氧化物“就地”引入,也就是在形成贵金属氧化物层以前引入,未公开具体的粉末形催化剂。
T.Ioroi等人[J.of Appl.Electrochemistry 31,1179-1183(2001)和J.of Electrochem.Soc.147(6),2018-2022(2000)]报道了IrO2/Pt电催化剂。这些催化剂通过碱沉积和随后热处理的方法以粉末形式制备。它们不含任何另外的无机氧化物。
US 2003/0057088 A1涉及使用Ir-Ru氧化物阳极催化剂的PEM水电解装置,所述的催化剂含有至少一种选自铁(Fe)、镍(Ni)和钴(Co)的金属氧化物。这些催化剂有低的氧过压。
JP 10-273791公开了通过氢氧化物共沉积来制备用于水电解的IrO2、RuO2和混合IrO2/RuO2催化剂。在500℃下热处理2小时。本发明人重复了这一方法,已发现这一方法制得的催化剂含有很粗的团聚颗粒物。因此,这些催化剂的BET表面积很低,它们的电化学活性不够高。此外,这些材料加工成催化剂涂料(ink)以及随后使用这样的催化剂涂料的任何涂覆和印制步骤都很困难。
E.Rasten等人在Proceedings Electrochemical Soc.,Vol.2001-23,page 151-164描述了热处理对用于PEM水电解装置的IrO2阳极催化剂的影响。这里描述的氧化铱催化剂根据ADAMS熔融法来制备[参考R.Adams and R.L.Shriner,J.Am.Chem.Soc.45,2171(1923)]。这一方法在于在硝酸钠的熔融盐熔体中加热氯化物前体(也就是IrCl3或H2IrCl6)。所述的盐熔体法产生大量有毒的氧化氮气体,并且必需以间歇法进行,产率低。此外,由E.Rasten等根据ADAMS法制备的催化剂颗粒很粗并且是团聚的。对于经退火的IrO2催化剂,报导的颗粒尺寸为30-100nm。
在DE 10211701 A1中,报导了一种就地固定水溶性纳米级金属氧化物胶体的方法。其中,对含有选自元素周期体系(PSE)的IIIb、IVb、Vb、VIb、VIIb、VIII、Ib或IIb副族金属的第二种金属的双金属氧化铱颗粒提出权利主张。这些催化剂可固定在无机氧化物载体上,例如氧化铝、氧化硅、氧化镁或氧化钛。在这一相当概括的公开内容中,没有无机载体材料的类型和性质以及无机氧化物在催化剂中的数量的详细内容。未公开所述催化剂用于水电解的应用。
发明概述
本发明的目的是要提供改进的基于贵金属氧化物特别是氧化铱的催化剂,它们适用于PEM水电解,有低的氧过压,有很低的贵金属载量以及可按环境上安全的方法来制备。此外,所述的催化剂必需有长的寿命并应使PEM电解装置有高的耐用性。
为了达到上述目的,提供了正如本发明的权利要求书中规定的改进的基于氧化铱的催化剂。
所要求的催化剂为复合的催化剂材料,它们包含氧化铱(IrO2和/或Ir2O3)和任选的氧化钌(RuO2和/或Ru2O3)与高表面积的无机氧化物(例如TiO2、Al2O3、ZrO2及其混合物)。本发明的氧化铱主要为氧化铱(IV)(IrO2),但不同数量的氧化铱(III)(Ir2O3)也可存在。术语“复合催化剂”指催化剂含有细分散在无机氧化物材料上或细分散在无机氧化物材料周围的氧化铱颗粒。
所要求的材料在PEM电解装置中用作阳极催化剂,在水电解中有很低的氧过压(也就是对于氧释放有低的启动电势),导致生产单位体积的氢有较低的比能耗。因此,在给定的电解池电压下有较高的氢生产速率。总之,它们可在比传统基于氧化铱的催化剂更低的电压下使水电解,所述传统的氧化铱基催化剂不含高表面积的无机氧化物。用所要求的贵金属氧化物催化剂制得的用于PEM水电解装置的涂覆有催化剂的薄膜(“CCMs”)和薄膜-电极组合件(“MEAs”)比现有技术材料有改进的性能。
因此,可设计出较小的电解装置体系,并且各种材料例如离聚物膜、贵金属和双极板的耗量较低。
发明详述
本发明涉及含有氧化铱和任选的氧化钌以及高表面积无机氧化物的贵金属氧化物催化剂。如果RuO2存在,Ru/Ir的原子比为4/1至1/4、优选约1/1。
本发明的氧化铱主要为氧化铱(IV)(IrO2),但也可存在不同数量的氧化铱(III)(Ir2O3),与制备方法有关。氧化钌可作为氧化钌(IV)存在,但也可存在少量氧化钌(III)。
通常,IrO2和RuO2都为导电的氧化物材料。为了得到最佳的催化剂性能,已发现按催化剂的总重计,无机氧化物的浓度必需限制到使其最大值为20重量%。如果无机氧化物的数量大于20重量%,那么催化剂的导电性和电极都受损。因此,按催化剂的总重计,加入的无机氧化物的数量小于20重量%、优选小于10重量%、最优选小于7.5重量%。
高表面积无机氧化物在本发明催化剂中的存在使催化剂在水电解中的性能和寿命得到改进。已发现为了得到更好的结果,无机氧化物的BET表面积应为50-400m2/g、优选100-300m2/g(BET表面积按DIN 66132测量)。
无机氧化物应为惰性的,在水中和在酸性环境中应有很低的溶解性。对于PEM电解装置的长寿命和高耐用性来说,这一点是重要的。通常,无机载体材料的水溶度应低于0.15g/l(<150mg/l)、优选低于0.05g/l(<50mg/l)。水溶度按EN ISO 787,第8部分在20℃下测量。较高的溶解度值导致在操作过程中无机氧化物逐渐从催化剂中洗脱出来。催化剂颗粒然后倾向于团聚。这就导致活性表面损失,并可使催化剂的活性下降。
适合的无机氧化物为热解的(“气相法制得的”)氧化物,例如由Degussa AG,Duesseldorf制造的TiO2、SiO2或Al2O3。优选的TiO2材料为锐钛矿变型,由Sachtleben Chemie GmbH(Duisburg)以商品名“Hombifine N”制造。优选的Al2O3材料为Puralox,由Sasol GermanyGmbH(Brunsbuettel)制造。其它适合氧化物载体的例子为Nb2O5、SnO2、掺杂的氧化锡(SnO2/F)、ZrO2、CeO2/ZrO2及其混合物和组合物。
在典型的制备方法中,将高表面积无机氧化物充分分散在水溶液中。然后加入铱前体化合物(六氯铱(IV)酸、氯化铱(III)或硝酸铱等)。然后将悬浮液加热到70-100℃,随后通过控制加入碱将pH值调节到6-10来使IrO2沉淀。过滤和洗涤以后,将催化剂干燥和焙烧。生成的催化剂有很高活性,有高的表面积、很低的团聚程度,可以很容易分散在催化剂涂料中,以便随后的涂覆过程。
为了制备混合Ir/Ru氧化物催化剂,将上述方法作了改变,将适合的Ir和Ru前体化合物共同加到无机氧化物在水的悬浮液中。适合的Ru化合物为水合RuCl3、硝酸亚硝酰钌(III)、醋酸钌(III)等。
催化剂材料的热处理在适合的间歇炉或带式炉中在空气气氛、还原气氛或惰性气氛中进行。典型的焙烧温度为300-800℃、优选300-500℃。典型的焙烧时间为30-120min。
在上述制备方法中,氧化铱颗粒物以很细的纳米级形式(也就是高度分散的形式)沉积在无机氧化物表面上。如果无机氧化物的表面积足够高,那么贵金属氧化物颗粒的分散在随后的热处理过程中仍是稳定的,颗粒物的烧结被抑制。这就得到高BET表面积的最后催化剂,继而得到高活性和高稳定性。当最后的氧化铱催化剂的BET表面积为40-100m2/g时,得到最佳的电化学性能结果。
如果没有所述的无机氧化物,就得到低表面积的粗团聚颗粒物,使电化学活性低(参考对比例)。
为了制备电极、涂覆有催化剂的薄膜(CCMs)和薄膜-电极组合件(MEAs),通过加入适合的溶剂和任选的离聚物材料将氧化铱催化剂加工成涂料或糊剂。可通过喷涂、印刷、流延或其它沉积方法将催化剂涂料沉积在气体扩散层(GDLs)、集流器、离聚物薄膜、空白PTFE板、隔离纸或隔板(separator plate)等上。通常,随后进行干燥,以便除去催化剂涂料中的溶剂。在用于PEM水电解装置的涂覆有催化剂的薄膜和MEAs中,将所要求的催化剂材料涂覆到MEA的阳极侧。典型的负载量为0.5-2.5mg p.m./cm2。在阴极侧上,使用标准的Pt催化剂(例如Pt/C或Pt-黑(Pt-Black))。阴极负载量为0.2-1mg Pt/cm2。
通过测量氧释放的开始电势(以伏计)和在1.5V下对NHE(以mA/mg计)的电流密度(以mA/cm2计)来测定催化剂材料的电化学性质。在这些试验中,将催化剂样品分散在5重量%Nafion®(Aldrich)的醇溶液中,然后固定在玻璃质碳电极上。在室温下在硫酸(c=0.5mol/l)中获得循环伏安曲线(voltammograms)。反电极为Pt,参考电极为Hg/Hg2SO4(Metrohm),扫描速度为10mV/s。取伏安曲线的第5次扫描,以产生伪静态条件。
用两个参数来确定电化学活性:(i)氧释放的开始和(ii)在恒定电压1.5V下对NHE的电流。用电势(V对NHE,y轴)对电流(mA/mg,x轴)的对数图的线性外延来确定氧释放的开始。
现采用以下实施例和对比例说明本发明,但不受以下实施例和对比例的限制。
实施例
实施例1
IrO2/TiO2(5重量%)的制备
将378.8mg二氧化钛(Hombifine N,Sachtleben ChemieGmbH;BET>300m2/g,20℃下的水溶解度<0.01g/l)在剧烈搅拌下加到装有112.5ml去离子水的1升烧杯中。随后,将29.7g六氯铱酸溶液(H2IrCl6,24.3重量%Ir;Umicore,Hanau/Germany)在搅拌下加到悬浮液中并用50ml去离子水稀释。然后将悬浮液加热到70℃。达到这一温度以后,加入50ml 0.1M的NaOH溶液,并另外用500ml去离子水稀释。
用10重量%NaOH将最终的pH值调节到7.0。将温度和pH值在相同的水平下保持约4h。最后,用过滤法分离产物,用2升去离子水洗涤。将催化剂在真空烘箱中干燥过夜。然后将产物在箱式炉中在400℃下在空气中焙烧。BET表面积仍很高,为66m2/g,表明所述的材料有极好的催化活性。表1列出催化剂的特性数据。
实施例2
IrO2/Al2O3(5重量%)的制备
将378.8mg氧化铝(Puralox SCFa-140,Sasol Germany GmbH,Brunsbuettel;BET=141m2/g)在剧烈搅拌下加到装有112.5ml去离子水的1升烧杯中。随后,将29.7g六氯铱酸溶液(H2IrCl6,24.27重量%Ir;Umicore,Hanau/Germany)在搅拌下加到悬浮液中并用50ml去离子水稀释。然后将悬浮液加热到70℃。达到这一温度以后,加入50ml 0.1M的NaOH溶液,并再用500ml去离子水稀释。
用10重量%NaOH将最终的pH值调节到7.5。将温度和pH值在相同的水平下保持约4h。最后,用过滤法分离产物,用1.5升去离子水洗涤。将催化剂在真空烘箱中干燥过夜。然后将产物在箱式炉中在400℃下在空气中焙烧1h。BET表面积仍很高,为59m2/g,表明所述的材料有极好的催化活性。
对比例
IrO2(没有无机氧化物)的制备
将150ml去离子水倒入2升烧杯中。将24.86g水合六氯铱酸水合物(38.65重量%Ir;Umicore,Hanau/Germany)溶于50ml去离子水中。将溶液在剧烈搅拌下加到烧杯中,再用50ml去离子水稀释两次。将溶液加热到70℃。达到这一温度以后,将4克NaOH溶于50ml去离子水中并在搅拌下加到溶液中。
用500ml去离子水稀释反应溶液,然后用10重量%NaOH将pH值调节到7.0。将温度和pH值在相同的水平下保持约4h。最后,用过滤法分离产物,用1升去离子水洗涤。将催化剂在真空烘箱中在100℃下干燥过夜。然后将材料在400℃下热处理。由于没有无机氧化物,BET表面积较低。特性数据列入表1。
表1
参数 | 实施例1 | 对比例 |
BET[m2/g] | 66 | 37 |
氧释放的开始电势[V] | 1.47 | 1.65 |
在1.5V下对NHE的电流密度[mA/mg] | 1.48 | 0.23 |
与实施例1(代表本发明)相比时,对比例表明很高的氧释放的开始电势(1.65V对实施例1的1.47V)。
这一点说明这一事实:在给定的电解池电压1.5V下的电流密度是很低的(0.23mA/mg对实施例1的1.48mA/mg)。所述数据清楚地说明本发明的催化剂的优良特性。
Claims (8)
1.用于水电解的催化剂,所述的催化剂包含氧化铱和无机氧化物,其中无机氧化物的BET表面积为50-400m2/g,按催化剂的总重计,其数量小于20重量%。
2.根据权利要求1的催化剂,还包含氧化钌,其数量使Ir/Ru原子比为4/1至1/4。
3.根据权利要求1或2的催化剂,其中无机氧化物选自氧化钛(TiO2)、氧化硅(SiO2)、氧化铝(Al2O3)、氧化锆(ZrO2)、二氧化锡(SnO2)、氧化铈、五氧化二铌(Nb2O5)、五氧化二钽(Ta2O5)和/或其组合。
4.根据权利要求1-3中任一项的催化剂,其中20℃下无机氧化物的水溶解度(按EN ISO 787,第8部分测定)小于0.15g/l、优选小于0.05g/l。
5.根据权利要求1-4中任一项的催化剂,其中氧化铱包含氧化铱(IV)、氧化铱(III)和/或其混合物。
6.制备权利要求1-4中任一项的催化剂的方法,所述的方法包括以下步骤:
a)将铱和任选钌的前体化合物在无机氧化物存在下溶于水溶液,
b)通过将混合物的pH值调节到6-10使氧化铱(任选与氧化钌一起)沉积,
c)分离和干燥催化剂,
d)在300-800℃的温度下热处理催化剂。
7.权利要求1-4中任一项的催化剂在PEM水电解装置的电极、涂覆有催化剂的薄膜(CCMs)和薄膜-电极组合件(MEAs)中作为阳极催化剂的应用。
8.权利要求1-4中任一项的催化剂在再生式燃料电池(RFC)、传感器、电解装置和其它电化学设备中的应用。
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CA2543256A1 (en) | 2005-06-02 |
KR20060100404A (ko) | 2006-09-20 |
NO331842B1 (no) | 2012-04-16 |
WO2005049199A1 (en) | 2005-06-02 |
US7976989B2 (en) | 2011-07-12 |
DE602004023231D1 (de) | 2009-10-29 |
DK1701790T3 (da) | 2010-01-25 |
NO20062368L (no) | 2006-05-24 |
US20070292744A1 (en) | 2007-12-20 |
EP1701790B1 (en) | 2009-09-16 |
KR101082859B1 (ko) | 2011-11-11 |
ATE442901T1 (de) | 2009-10-15 |
JP2007514520A (ja) | 2007-06-07 |
CA2543256C (en) | 2010-06-29 |
US8263290B2 (en) | 2012-09-11 |
JP5199575B2 (ja) | 2013-05-15 |
US20110223523A1 (en) | 2011-09-15 |
CN1874841B (zh) | 2010-09-15 |
EP1701790A1 (en) | 2006-09-20 |
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