CN1795293A - 用于氧还原的催化剂 - Google Patents
用于氧还原的催化剂 Download PDFInfo
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- CN1795293A CN1795293A CNA200480014526XA CN200480014526A CN1795293A CN 1795293 A CN1795293 A CN 1795293A CN A200480014526X A CNA200480014526X A CN A200480014526XA CN 200480014526 A CN200480014526 A CN 200480014526A CN 1795293 A CN1795293 A CN 1795293A
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- catalyzer
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- ruthenium
- hydrogen sulfide
- atmosphere
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- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 230000009467 reduction Effects 0.000 title claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000001301 oxygen Substances 0.000 title claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 32
- 238000009792 diffusion process Methods 0.000 claims abstract description 29
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 29
- 229910052707 ruthenium Inorganic materials 0.000 claims description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 23
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- 238000005987 sulfurization reaction Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- JFNYHNBFNULGPQ-UHFFFAOYSA-N [Ru].S(O)(O)=O Chemical compound [Ru].S(O)(O)=O JFNYHNBFNULGPQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 8
- 238000010790 dilution Methods 0.000 claims 6
- 239000012895 dilution Substances 0.000 claims 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 239000000428 dust Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 150000003304 ruthenium compounds Chemical class 0.000 claims 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000000935 solvent evaporation Methods 0.000 claims 1
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 239000006229 carbon black Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- -1 ruthenium oxide compound Chemical class 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
本发明涉及新型硫化钌催化剂,和在工业电解池内用于氧还原的掺入所述硫化钌催化剂的气体扩散电极。该催化剂高度抗腐蚀,于是导致尤其适合在氧去极化的含水盐酸电解中使用。
Description
背景技术
HCl水溶液的电解是回收高价值氯气的公知方法。含水盐酸是丰富的化学副产物,特别是在利用氯作为反应物的化学装置内,在此情况下,在电解池的阳极隔室内释放的氯可作为原料循环到化学装置内。当用耗氧的气体扩散电极替代标准的氢气释放阴极时,由于有关的能耗下降导致电解变得极具吸引力。气体扩散电极在这一情况下成功地操作的能力关键取决于催化剂的性质和性能,且该取决于气体扩散电极的结构。
铂通常被视为在宽范围的条件下用于电还原氧的最有效的催化剂;具有铂基催化剂的气体扩散电极的活化是本领域公知的,且在许多种类的燃料电池和电解池中具有广泛的应用。然而,含水HCl电解的情况下使用铂作为阴极催化剂具有一些严重的缺点,因为气体扩散阴极不可避免地至少部分与液体电解质接触,所述液体电解质含有氯离子和溶解的氯。首先铂易于氯离子中毒,氯离子中毒会其对氧还原的活性产生负面影响;第二种中毒来源由污染物质组成,特别是有机物质,在大多数情况下,它们溶解在经历电解的副产物盐酸内。甚至更加重要的是,盐酸和溶解的氯的配位作用将铂金属变为被溶解的可溶盐,从而使得该材料不适合在气体扩散电极中使用。此外,在周期性切断电解池的过程中,必须极仔细地注意,否则阴极电势的突变,结合高的腐蚀性化学环境,会引起大量催化剂溶解,和剩余部分的部分失活。尽管考虑到额外的成本可安装计划切断电解池的特制工序,但由于不可预测的原因,如电网的电源短路导致在突然、不可控的切断情况下无计可施。
因一些铑基催化剂的公开部分减少了这些问题,已证明铑基催化剂在氧的还原反应方面活性不如铂,但较少地受到存在于该体系内的氯离子的影响,从而一旦掺入到气体扩散电极内就操作电压来说,得到更加可接受的结果。特别地,在美国专利5958197中公开的铑金属/氧化铑催化剂在溶解的氯和氧存在下还被证明相当抗盐酸环境,尽管它要求麻烦的活化工序来充分形成其抗腐蚀形式。
美国专利6149782公开了基于硫化铑的抗性甚至更大的催化剂,它不要求任何活化步骤,且显示出额外的优点:对酸性原料内的有机污染物不敏感。
尽管这些催化剂在与含水盐酸去极化电解有关的苛刻环境内,在活性和抗化学性两方面均显示出非常良好的性能,但在有效的商业利用度方面来说,其价格和可获得性是很大的问题。本领域的专家公知的是,铑是迄今为止最昂贵的贵金属,其价格甚至超过锇之一,且是例如钌和铱的一个数量级;尽管去极化的含水盐酸电解是具有大的市场需求的技术,但现有技术催化剂的价格太高,以致于不可能成功地商业化。
在酸性介质内的氧还原中可用的价格合理的贵金属当中,钌是一种显然的选择,其活性与铑之一相当,和其价格平均低约20倍。通过由RuCl3的含水沉淀制备的RuO2是公知的催化剂;遗憾的是,在氯饱和的盐水介质内,其(在热稳定化之前的)化学稳定性差,和催化剂在相对短的时间内溶解掉。其它硫化物看起来具有相同的命运,除非化学稳定化该材料。当今,藉助含水沉淀制备的硫化铑提供良好的备用品(参见美国专利6149782)。以同样方式获得的硫化钌证明在氯饱和的盐酸环境内几乎不稳定。在现有技术中公开的用于氧还原的唯一类似的催化剂,Chevrel相类催化剂,亦即MoxRuyS/C在升高的温度和酸性浓度下也不稳定(参见J.Chem.Soc.,Faraday Trans.,1996,92,4311)。
发明目的
本发明的目的是提供克服了现有技术缺点的用于氧还原的催化剂,其在溶解的氯和任选地溶解的氧存在下,在盐酸环境内化学稳定。
另一方面,本发明的目的是提供在去极化盐酸电解池内使用的、掺入用于氧还原的催化剂内的气体扩散电极。
在进一步的方面中,本发明的目的是提供生产克服了现有技术缺点的用于氧还原的催化剂的方法,其在溶解的氯和任选地溶解的氧存在下,在盐酸环境内化学稳定,和掺入用于氧还原的催化剂内的气体扩散电极的生产方法。
根据下述详细说明,本发明的这些和其它目的与优点将变得显而易见。
发明描述
在第一方面中,本发明由承载的硫化钌的化学稳定形式组成,这是因为本发明的催化剂涉及在去极化的盐酸电解用的气体扩散电极内使用,在下述说明中,“化学稳定形式”拟指在盐酸环境内,亦即在溶解的氯和任选地溶解的氧存在下化学稳定。
在第二方面中,本发明的气体扩散电极包括导电网,优选碳布,其中用任选地与疏水粘合剂混合的承载硫化钌催化剂的化学稳定形式涂布所述导电网。
在第三方面中,生产本发明催化剂的方法包括用钌和任选地另一过渡金属的前体对导电载体进行初始润湿(incipient wetness)浸渍,干燥浸渍过的载体,并在含硫化氢的氛围下处理所得产物。
在第四方面中,生产本发明催化剂的方法包括在含硫化氢的氛围内,使承载的氧化钌化合物,任选地碳承载的RuO2进行硫化反应。
在第五方面中,生产本发明的气体扩散电极的方法包括用任选地与疏水粘合剂混合的本发明催化剂涂布导电网,和任选地烧结该涂布网。
在一个优选的实施方案中,本发明的催化剂是通式RuxSy的二元化合物。在更优选的实施方案中,本发明的催化剂是通式RuxMyS的三元化合物,其中M是普通的过渡金属。在另一优选的实施方案中,本发明的催化剂是钌和大于一种其它普通的过渡金属的混合硫化物。在仍更优选的实施方案中,本发明的催化剂是钌和选自钴、镍、铼、铬、钼和铱中的另一过渡金属的三元硫化物。尽管藉助湿法化学由钌前体的水溶液与硫化氢,或者由钌前体与元素硫的有机溶液常规地获得的本领域以前公知的硫化钌催化剂,在含溶解的氯的盐酸内,在化学稳定性方面,显示出差的性能,但发明人令人惊奇地发现,藉助气固反应获得的硫化钌催化剂在相同环境内稳定,同时保留满意的电催化活性。在一个优选的实施方案中,通过在导电惰性载体,如炭黑上承载催化剂,有助于将本发明的催化剂掺入到气体扩散电极结构内。在此情况下,优选碳载体是高表面积的炭黑,例如表面积超过120m2/g的炭黑。
在一个优选的实施方案中,本发明的催化剂是通式RuxCoyS的钌和钴的硫化物的化学稳定形式,其中Ru∶Co原子比优选介于1∶5至5∶1,更优选约3∶1,例如介于2.8∶1至3.2∶1。
根据非常类似于美国专利6149782中公开的制备硫化钌所使用的方法非常类似的工序,也就是说,通过任选地在导电惰性载体存在下,在钌前体,通常氯化物的水溶液内喷洒硫化钌,获得现有技术的硫化钌催化剂。然后正常地干燥沉淀并热处理。然而,以这一方式获得的钌催化剂几乎在盐酸环境内不稳定,特别是若存在溶解的氯的话。通过气固反应相反地获得本发明的硫化钌催化剂:导电惰性载体,优选高表面积的炭黑没有分散在前体的水溶液内,而是进行用该前体的水溶液进行初始润湿浸渍。为此,有效的是,前体溶液含有2-丙醇,或等价物,优选与水混溶的挥发性溶剂。前体溶液可喷洒在粉末载体上,或者可将溶液缓慢地加入到载体内,直到它可被吸收。当载体的初始润湿浸渍完成时,必须仔细干燥所得浸渍载体,优选在真空下,在超过90℃的温度下。这一操作通常要求数小时;在含硫化氢的氛围内,优选在流动反应器内,最后对所得干燥产品进行硫化反应。
在另一优选的实施方案中,获得本发明催化剂的起始材料是承载的氧化钌,例如本领域已知的碳承载的二氧化钌。在含硫化氢的氛围内,优选在流动反应器内,对这一承载的氧化钌进行气固硫化反应,如同在前一情况中一样。
在这两种情况下,优选用氮或者用另一惰性载体稀释硫化氢;优选使用摩尔比介于0.5至4的氮/硫化氢混合物。
可以以数种方式实现在气体扩散电解结构(其用作去极化盐酸电解的阴极)内掺入本发明的催化剂,这是本领域技术人员公知的;在一个优选的实施方案中,通过用与第一聚合物粘合剂,例如疏水粘合剂任选地混合的含本发明催化剂的糊剂涂布导电网,例如碳布,从而获得本发明的气体扩散电极。作为粘合剂,优选使用全氟化粘合剂如PTFE,但也可使用部分氟化或非氟化的粘合剂。催化剂/粘合剂混合物可直接施加到导电网上,获得所谓的“直流(flow-through)”气体扩散电极;在另一实施方案中,可事先用导电填料(例如炭黑)和第二粘合剂的混合物涂布导电网的一个或两个侧面。在一些情况下,第一和第二粘合剂可以是相同材料。一旦用催化剂/粘合剂混合物涂布,则通常在其使用之前干燥气体扩散电极;在一些情况下,也可根据气体扩散电极制造领域的公知工序,有利地在使用之前烧结该电极。尽管如此,发明人令人惊奇地发现,当将本发明的催化剂掺入到气体扩散电极结构中时,可有利地省去烧结步骤。尽管当没有烧结时,本发明的催化剂非常稳定,但可进行烧结以改进整个气体扩散电极结构的长期稳定性。在此情况下,当在还原氛围内(例如氢气压力下),进行从环境温度陡增到约100-120℃的第一加热,同时在氩气或其它惰性气体下进行最后的热处理(通常达到300-350℃的温度)时,获得最好的结果。
在下述实施例中,描述了数种优选实施方案以阐述本发明。然而,要理解,本发明不限于具体的实施方案。
实施例1
用RuCl3·3H2O(37.8%Ru)和Co(NO3)3·6H2O(20.2%Co)前体盐的2-丙醇溶液对10g获自Cabot Corp./USA、表面积为约230m2/g的Vulcan XC-72炭黑粉末进行初始润湿浸渍;其中使用3∶1(Ru∶Co)的原子比。将该溶液缓慢加入到炭黑粉末中,只要所倾倒的液体可被完全吸收即可。在真空烘箱内,在110℃下蒸发溶剂并干燥过夜。所得产物随后在流动反应器内,在400℃下,在2∶1氮和硫化氢氛围下,硫化1小时的时间段。在气固反应完成之后,还维持相同的氛围,同时冷却样品。获得炭黑承载的RuxCoyS催化剂,这通过XRD数据来证实。
实施例2
在10g Vulcan XC-72粉末上重复实施例1相同的工序,唯一区别在于前体盐溶液仅含有在2-丙醇内的RuCl3·3H2O,且不添加钴前体。结果获得炭黑承载的RuxSy催化剂,这通过XRD数据来证实。
实施例3
RuO2/C是本领域公知的,它通过在碳存在下,在pH 5下,用酸式碳酸盐,从RuCl3中沉淀,或者通过同样在碳存在下,涉及亚硫酸钌(H3Ru(SO2)2OH)与过氧化氢(H2O2)的氧化反应而制备。在本发明的情况下,根据本发明,藉助气固反应,将这类催化剂转化成稳定形式的硫化钌。将20g Vulcan XC-72炭黑粉末分散在水溶液内,向其中添加20g RuCl3·1.5H2O。通过缓慢添加浓度为6.7wt%的NaHCO3溶液沉淀氧化钌中间体。干燥所得产物,随后在流动反应器内,在400℃下,在2∶1氮和硫化氢氛围下,硫化2小时的时间段,在气固反应完成之后,还维持相同的氛围,同时冷却样品。获得炭黑承载的RuxSy催化剂,这通过XRD数据来证实。
对比例1
将气体硫化氢喷洒在含精细分散的Vulcan XC-72炭黑粉末的RuCl3·3H2O水溶液内。在氩气氛围中,在650℃下焙烧所得沉淀2小时。结果获得炭黑承载的RuxSy催化剂,这通过XRD数据来证实。
实施例4
在盐酸电解的相同化学环境内,但在更加苛刻得多的温度条件下对实施例1、2和3以及对比例1的催化剂进行相同的加速稳定性试验。最初在室温下,将每一催化剂样品浸渍在100ml来自实验室HCl电解池的阳极电解液母液内,所述阳极电解液母液由HCl水溶液与溶解的氯组成。然后加热含母液分散的催化剂样品的容器,并保持在沸腾温度(约103℃)下20分钟。在完成试验之后,含实施例1、2和3的催化剂的容器内的的母液仍然无色,而含对比例1的催化剂的母液变为褐色。随后对这三种溶液的分析表明,在含实施例1、2和3的催化剂的容器情况下,仅仅痕量的钌,而在对比例1的情况下,分析表明发生大量的钌浸出。
实施例5
混合实施例1和2的催化剂到PTFE分散液中并掺入到在碳布上的常规直流气体扩散电极结构内。在施加PTFE/催化剂糊剂到布料上并将其干燥之后,将两个电极的每一个切割成四片,其中三片进行三种不同的烧结工序。由此获得下述样品:
样品1a和1b:分别为RuxCoyS和RuxSy,在H2中烧结到最多110℃,保持该温度30分钟,然后转变为Ar并陡增到最多335,保持该温度15分钟。
样品2a和2b:分别为RuxCoyS和RuxSy,在Ar中烧结到最多335℃,保持该温度15分钟。
样品3a和3b:分别为RuxCoyS和RuxSy,在空气中烧结到最多335℃,保持该温度15分钟。
样品4a和4b:分别为未烧结的RuxCoyS和RuxSy。
所有这8个样品用0.5-0.8mg/cm2的全氟烃离聚物溶液(这去极化盐酸电解领域中是常规的)涂布。在HCl电解池阳极电解液母液内,对8种离聚物涂布的样品进行相同的稳定性试验20分钟,同时在沸腾的电解质内鼓入氧,和相应的溶液显示出下述颜色:
样品1a:非常浅的黄色
样品1b:无色
样品2a:暗黄色
样品2b:浅橙色
样品3a:亮橙色
样品3b:暗橙色/褐色
样品4a:无色
样品4b:无色
随后发现这些定性数据与藉助XRF分析在不同溶液上测定钌获得的那些相匹配。与其它烧结工序相比,在氢气内烧结接着氩气下烧结的电极远远地要稳定得多,且空气烧结得到最差的结果。尽管如此,令人惊奇的是,证明非烧结的电极至少与在氢气中烧结的那些一样稳定;非烧结的电极的稳定性数据与在掺入到气体扩散电极结构内之前的原始催化剂的稳定性数据相匹配。
实施例6
根据美国专利6149782(样品0)的教导,将相当于样品1a、1b、2a、3a和4a的电极制备成50cm2的尺寸,并与用于盐酸电解的标准RhSx电极相比较。在50cm2的活性区的实验室电池内,相对于标准阳极测试作为耗氧阴极的这种电极,从而利用来自异氰酸酯装置的副产物盐酸水溶液。在两种不同的电流密度,亦即3和6kA/m2下记录总的电池电压,并在表1中报道了相应的数值。
表1
样品ID | 在3kA/m2下的电压 | 在6kA/m2下的电压 |
0 | 1.10 | 1.41 |
1a | 1.16 | 1.41 |
1b | 1.16 | 1.44 |
2a | 1.22 | 1.56 |
3a | 1.16 | 1.50 |
4a | 1.17 | 1.49 |
所有测试的电极样品显示出可接受的催化活性,从而相对于现有技术的硫化钌电极(样品0),导致适中或者可忽略不计的电压增加。
上述说明不应当理解为限制本发明,可在没有脱离其精神的情况下根据不同的实施方案实践本发明,和本发明的范围仅仅通过所附权利要求来限定。
在本发明的下述说明和权利要求中,措辞“包括”极其变体如“含”和“包含”不打算排除其它元素或额外的组分的存在。
Claims (45)
1.一种用于氧还原的催化剂,它包括在溶解的氯和任选地溶解的氧存在下,在盐酸环境内化学稳定的硫化钌。
2.权利要求1的催化剂,其中所述硫化钌承载在任选地由表面积超过120g/m2的碳组成的导电惰性载体上。
3.权利要求2的催化剂,其中所述碳为Vulcan XC-72。
4.权利要求1的催化剂,其中所述硫化物是承载在碳上的RuxSy。
5.权利要求4的催化剂,它通过用任选地含氯化钌的钌的前体盐初始润湿浸渍所述碳,蒸发溶剂,并在任选地用惰性载体气体稀释的硫化氢氛围中处理所得产物而获得。
6.权利要求4的催化剂,它通过在所述碳上含水沉淀氧化钌,在任选地用惰性载体气体稀释的硫化氢氛围中干燥并处理所得产物而获得。
7.权利要求1的催化剂,其中所述硫化物具有通式RuxMyS,其中M是过渡金属。
8.权利要求7的催化剂,其中所述金属M选自Ni、Re、Cr、Mo、Ir。
9.权利要求1的催化剂,其中所述硫化物是承载在碳上的RuxCoyS。
10.权利要求9的催化剂,其中Ru∶Co的原子比介于0.2至5,优选介于2.8至3.2。
11.权利要求7的催化剂,它通过用钌和过渡金属M的前体盐,任选地氯化物初始润湿浸渍所述碳,蒸发溶剂,并在任选地用惰性载体气体稀释的硫化氢氛围中处理所得产物而获得。
12.权利要求9或10的催化剂,它通过用钌和钴的前体盐初始润湿浸渍所述碳,蒸发溶剂,并在任选地用惰性载体气体稀释的硫化氢氛围中处理所得产物而获得。
13.权利要求12的催化剂,其中所述前体盐包括RuCl3和Co(NO3)2中的至少一种。
14.权利要求11-13任何一项的催化剂,其中所述溶剂包括2-丙醇。
15.权利要求11-13任何一项的催化剂,其中在高于90℃的温度下,在真空下进行所述溶剂蒸发。
16.权利要求11-13任何一项的催化剂,其中在流动反应器内进行在硫化氢氛围中的所述处理。
17.权利要求11-13任何一项的催化剂,其中在超过100℃,优选介于300至500℃的温度下进行在硫化氢氛围中的所述处理。
18.权利要求11-13任何一项的催化剂,其中在超过30分钟,优选介于1至4小时的时间内延长在硫化氢氛围中的所述处理。
19.权利要求11-13任何一项的催化剂,其中所述惰性载体气体是氮,和所述氮对所述硫化氢的摩尔比介于0.5至4。
20.一种气体扩散电极,它包括导电网,其中将前述任何一项权利要求的催化剂施加在所述导电网的至少一面上。
21.权利要求20的气体扩散电极,其中所述导电网是碳布。
22.权利要求20的气体扩散电极,其中混合所述催化剂与任选全氟化疏水粘合剂。
23.生产用于氧还原的催化剂的方法,该方法包括下述步骤:用含钌的至少一种前体的溶液对导电载体进行初始润湿浸渍,干燥浸渍过的载体,并在任选地用惰性载体气体稀释的硫化氢氛围中处理所得产物。
24.权利要求23的方法,其中所述溶液还含有过渡金属的前体。
25.权利要求24的方法,其中所述过渡金属选自Co、Ni、Re、Cr、Mo、Ir。
26.权利要求25的方法,其中所述溶液含有RuCl3和Co(NO3)2中的至少一种。
27.权利要求26的方法,其中在所述溶液内Ru∶Co的摩尔比介于0.2至5,优选介于2.8至3.2。
28.权利要求23的方法,其中所述溶液包括2-丙醇。
29.权利要求23的方法,其中在高于90℃的温度下,在真空下进行所述干燥。
30.生产用于氧还原的催化剂的方法,该方法包括下述步骤:在分散在水溶液内的导电载体上沉淀氧化钌,干燥浸渍过的载体,并在任选地用惰性载体气体稀释的硫化氢氛围中处理所得产物。
31.权利要求23或30的方法,其中在流动反应器内进行在硫化氢氛围中的所述处理。
32.权利要求23或30的方法,其中在超过100℃,优选介于300至500℃的温度下进行在硫化氢氛围中的所述处理。
33.权利要求23或30的方法,其中在超过30分钟,优选介于1至4小时的时间段内延长在硫化氢氛围中的所述处理。
34.权利要求23或30的方法,其中所述惰性载体气体是氮,和所述氮对所述硫化氢的摩尔比介于0.5至4。
35.权利要求30的方法,其中所述氧化钌是通过使含钌化合物,任选地RuCl3的水溶液,与酸式碳酸钠反应,或者通过使亚硫酸钌与过氧化氢反应而沉淀的RuO2。
36.生产权利要求20-22任何一项的气体扩散电极的方法,它包括用任选地与第一疏水粘合剂混合的所述催化剂涂布所述导电网的至少一个侧面。
37.权利要求36的方法,其中所述导电网是碳布。
38.权利要求36的方法,其中所述第一疏水粘合剂是全氟化的。
39.权利要求36的方法,其中在使用所述催化剂的所述涂布之前,用碳粉和第二任选地全氟化疏水粘合剂的混合物涂布所述导电网的至少一个侧面。
40.权利要求36的方法,进一步包括最终的烧结步骤。
41.权利要求40的方法,其中所述最终的烧结步骤包括在氢气氛围中,在从室温到中间温度下加热,和随后在惰性氛围中,在从所述中间温度到最终温度下加热。
42.权利要求41的方法,其中所述中间温度介于100至120℃。
43.权利要求41的方法,其中所述最终温度介于300至350℃。
44.权利要求41的方法,其中所述惰性氛围是氩气氛围。
45.权利要求20-22任何一项的气体扩散电极在去极化盐酸电解池内作为供氧气体扩散阴极的用途。
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CN108823602A (zh) * | 2018-07-12 | 2018-11-16 | 北京化工大学 | 一种硫化钌颗粒复合材料、其制备方法及用途 |
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CN101589178B (zh) * | 2007-02-22 | 2011-06-01 | 德诺拉工业有限公司 | 用于氧气的电化学还原的催化剂 |
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CN107949662B (zh) * | 2015-03-30 | 2020-01-17 | 德诺拉工业有限公司 | 用于碱性水电解池的隔膜-电极组件 |
CN112368073A (zh) * | 2018-06-12 | 2021-02-12 | 国立研究开发法人科学技术振兴机构 | 催化剂及其使用方法 |
CN112368073B (zh) * | 2018-06-12 | 2024-04-09 | 国立研究开发法人科学技术振兴机构 | 催化剂及其使用方法 |
US11965255B2 (en) | 2018-06-12 | 2024-04-23 | Japan Science And Technology Agency | Catalyst and method of use thereof |
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