CN100428988C - 在不含二价硫离子的含水环境中贵金属硫化物催化剂的合成 - Google Patents
在不含二价硫离子的含水环境中贵金属硫化物催化剂的合成 Download PDFInfo
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- CN100428988C CN100428988C CNB2005800035175A CN200580003517A CN100428988C CN 100428988 C CN100428988 C CN 100428988C CN B2005800035175 A CNB2005800035175 A CN B2005800035175A CN 200580003517 A CN200580003517 A CN 200580003517A CN 100428988 C CN100428988 C CN 100428988C
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title 1
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 239000005864 Sulphur Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000010948 rhodium Substances 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 229910052703 rhodium Inorganic materials 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical group [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 3
- 229940075933 dithionate Drugs 0.000 claims description 2
- JEIULZGUODBGJK-UHFFFAOYSA-L trisulfane-1,3-disulfonate Chemical compound [O-]S(=O)(=O)SSSS([O-])(=O)=O JEIULZGUODBGJK-UHFFFAOYSA-L 0.000 claims description 2
- KRURGYOKPVLRHQ-UHFFFAOYSA-L trithionate(2-) Chemical compound [O-]S(=O)(=O)SS([O-])(=O)=O KRURGYOKPVLRHQ-UHFFFAOYSA-L 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 3
- 159000000000 sodium salts Chemical group 0.000 claims 3
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- -1 sulphide ions Chemical class 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229940046892 lead acetate Drugs 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- HAEPBEMBOAIUPN-UHFFFAOYSA-L sodium tetrathionate Chemical compound O.O.[Na+].[Na+].[O-]S(=O)(=O)SSS([O-])(=O)=O HAEPBEMBOAIUPN-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- HPQYKCJIWQFJMS-UHFFFAOYSA-N tetrathionic acid Chemical compound OS(=O)(=O)SSS(O)(=O)=O HPQYKCJIWQFJMS-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002999 depolarising effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 description 1
- KWUDHYDXPZUANY-UHFFFAOYSA-N [S].[Mo].[Rh] Chemical compound [S].[Mo].[Rh] KWUDHYDXPZUANY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical compound C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- KRURGYOKPVLRHQ-UHFFFAOYSA-N trithionic acid Chemical compound OS(=O)(=O)SS(O)(=O)=O KRURGYOKPVLRHQ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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Abstract
本发明涉及一种催化剂,特别是贵金属硫化物电催化剂,其通过使至少一种贵金属前体与含硫物质在基本上不存在二价硫离子的含水环境中反应而获得,以及该催化剂的制备方法。
Description
技术领域
本发明涉及催化剂,特别涉及贵金属硫化物电催化剂及其制备方法。
发明背景
贵金属硫属元素化物广泛已知于电催化领域;特别是,普遍地将基于铑和钌的硫化物的电催化剂掺入气体扩散电极以在高腐蚀环境中用作氧化-还原阴极,例如在盐酸的去极化电解中。
通过将硫化氢喷雾在相应贵金属前体(通常是氯化物)的水溶液中来制备用于电催化的贵金属硫化物,例如在US6,149,782中所公开的内容,其涉及硫化铑催化剂。在水溶液中与硫化氢所进行的贵金属硫化物催化剂的合成常规地是在导电载体的存在下进行,在多数情况下所述导电载体由碳颗粒组成。以这样的方式,贵金属硫化物选择性地沉淀在碳颗粒的表面,因而所得产品是碳负载催化剂,其特别适于掺入到特征在于在降低的贵金属负载下具有高效率的气体扩散电极结构中。高表面积碳黑,如从Cabot Corp./USA获得的Vulcan XC-72,特别适于该范围。
一个不同的制备碳负载的贵金属硫化物催化剂的过程包括:用贵金属前体盐,例如贵金属氯化物,初始湿度浸渍碳载体,随后蒸发溶剂和在稀释的硫化氢氛围内、在环境温度或升高的温度下进行气相反应,从而以稳定相形成硫化物。例如,其公开于未审批的临时申请60/473,543中,该申请涉及硫化钌催化剂。
在贵金属为铑的情况下,在使用之前,应对如此获得的贵金属硫化物催化剂在通常范围为300-700℃的温度下进行适当的稳定化热处理。在其它的情况下,低至150℃的温度对于适当的热处理来说已经是足够的。
尽管这些催化剂在氧化还原活性和高腐蚀环境下的稳定性方面显示了良好性能,这使得它们实际上对于在盐酸电解中的氧化还原催化来说成为唯一可用的物质,但是一些不便之处使它们经由硫化氢的生产路线受到了影响。
第一,在它们的合成中使用高度危险的物质,如硫化氢,其是易燃且有毒的气体,这引起了严重的对于环境和人类健康的关注。对于硫化氢的处理是件非常棘手的事情,人们仅能借助于昂贵的安全检测来进行处理。
第二,在存在游离二价硫离子(sulphide ion)的环境中的沉淀,会导致以可变的化学计量形成化合物,并且这会妨碍所需催化剂的可再生产性,尤其在与某些贵金属反应的情况下;此外,二价硫离子是有毒且环境不友好的物质。
用于硫化物沉淀的其它普通的反应物,如多硫化物、硫代乙酸或硫代乙酰胺,它们不如硫化氢的危险性大,但是在含水环境中的反应路径仍然要在这些化合物预电离或水解以提供不希望的游离二价硫离子之后进行。
由于游离二价硫离子和尤其是高度易燃且高毒性的硫化氢类物质的存在,所以为了贵金属硫化物催化剂的生产能成功地规模化,并且实际上为了潜在巨大的电化学工艺(如盐酸的去极化电解)的商业化,迫切需要一种可供选择的用于合成在氧化还原催化中使用的贵金属硫化物的路线。
发明目的
本发明的一个目的是通过在不含硫化氢并且基本上不含二价硫离子物质的含水环境中进行沉淀,提供一种贵金属硫化物催化剂,所述催化剂任选地负载在碳颗粒上。
本发明的另一个目的是提供一种在含水环境中避免使用高易燃性和高毒性物质的制备贵金属硫化物催化剂的方法。
发明描述
在一方面,本发明涉及一种优选负载于高表面积碳黑上的贵金属硫化物催化剂,其通过使相应的贵金属前体,优选氯化物,与含硫物质(thionic species)在水溶液中反应而获得。对于高表面积碳黑,是指表面积超过50m2/g的碳黑物质。对于含硫物质,是指含有硫官能团,如硫代硫酸盐、硫羰酸(thionic acid)及其酸衍生物的任何化学物质。在一个优选的实施方案中,反应在基本上不含二价硫离子的水溶液中进行。本发明的催化剂可以是任意贵金属的硫化物或者甚至是至少一种贵金属与一种或多种共同元素(co-element)的混合硫化物;在一个优选的实施方案中,这样的贵金属选自钌、铑、铂、铱和钯。
在最优选的实施方案中,在使用之前将本发明的催化剂于150-700℃的温度下进行热处理。
本发明的催化剂特别适于掺入在导电网如碳布或金属网上生产的气体扩散电极结构,尤其是用于盐酸的氧-去极化电解的气体扩散阴极或在高度腐蚀环境中的其它耗氧阴极。
在另一方面,本发明涉及在不存在硫化氢和在基本上不含游离二价硫离子的环境中制备贵金属硫化物催化剂的方法,所述方法包括:使贵金属前体(任选地为氯化物)的溶液与含有含硫物质的水溶液反应,其中含硫物质优选为钠或铵的硫代硫酸盐或连四硫酸盐溶液。本发明的贵金属硫化物催化剂可以含有单独贵金属的硫化物,或者一种贵金属与一种其它贵金属或非贵金属的混合硫化物。因此,贵金属前体溶液可以含有其它贵金属或非贵金属前体。可选择地,混合硫化物催化剂可以通过使一种贵金属前体溶液与含有第二种贵金属或非贵金属的含硫物质反应而制备。
已知,一般来说,硫代硫酸盐阴离子可通过歧化反应得到一个二价硫离子和一个硫酸根离子作为产品,从而形成了硫化物:
S2O3 -2+H2O→S-2+SO4 2-+2H+
然而,发明人已经发现,在特定的条件下,从硫代硫酸盐开始的贵金属(例如,钌、铑、铂、铱或钯)硫化物的合成在进行中不会释放出任何能检测得到的游离二价硫离子。
不希望本发明束缚于任何特定理论,可以假定该过程通过金属离子与两个硫原子之一直接反应而进行,造成剩余部分分解。
在此后记载的实施例中,发明人已经更加明确地观察到优选的路径是部分歧化的路径,已知其还可被当作S2O3 -2物质的复分解,其中按照下面的化学计量两个S原子是不等价的:
S2O3 -2→S-2·SO3
发明人特别发现,当将含有反应物的水溶液带入沸腾或处于50℃-100℃的温度范围内时,硫代硫酸盐与一些过渡金属在0.1-4.0之间的pH下反应以形成金属硫化物。
当将硫代硫酸盐用于硫化物的沉淀时,为了提供所需的硫化物催化剂,反应物的添加顺序是关键的。实际上,如果首先将硫代硫酸盐添加至不含要被沉淀的金属的酸性溶液中时,将发生下面的歧化反应:
2H++S2O3 -2→S0+SO2+H2O
相反,如果在添加硫代硫酸盐之前金属离子就存在于溶液中,后者会显示出被稳定化从而延迟歧化反应,并且因此造成硫化物的复分解。对于其它类型的含硫物质,反应物的添加顺序反而不那么重要。例如,连四硫酸盐在酸性溶液中非常稳定并且不会发生上面所看到的类型的歧化反应。
在先前的领域没有提到由其它硫羰酸衍生物如连二硫酸盐(S2O6 -2)、连三硫酸盐(S3O6 -2)、连四硫酸盐(S4O6 -2)、连五硫酸盐(S5O6 -2)或连七硫酸盐(S7O6 -2)进行硫化物的沉淀,并且其路径还不完全清楚。然而,在与硫代硫酸盐的沉淀条件相同的条件下,发明人可以从所有这些物质得到各种贵金属硫属元素化物,并且在该过程的任何步骤均未检测到游离二价硫离子。特别优选使用连四硫酸盐物质(例如连四硫酸钠)进行贵金属或混合金属硫化物的沉淀,因为连四硫酸钠是普及且便宜的商业化产品。在这种情况下,与过渡金属的反应也是发生在0.1-4.0(最优选1.0-4.0)之间的pH范围,以及在50℃-沸腾温度的温度范围内。
在一个优选的实施方案中,在高表面积碳颗粒或其它惰性且优选导电的颗粒存在下进行反应以获得负载的贵金属硫化物催化剂。在一个优选的实施方案中,以不连续的等分试样方式,例如2-10等量的等分试样以15秒-10分钟的间隔添加含硫反应物的溶液。在一个优选的实施方案中,在将含硫反应物溶液添加至贵金属前体溶液中之后,将所得溶液加热至沸腾温度直到反应完成(根据所选择的前体和反应条件,反应可持续5分钟至两小时)。优选反应之后上清液颜色变化,从而可容易地检测反应的完成。
在一个最优选的实施方案中,本发明的方法进一步包括:在使用之前将所获得的产品于150-700℃进行热处理。
下面实施例的目的是为了更好地阐明本发明,而不构成对其范围的限制,其范围仅由所附的权利要求定义。
实施例1
在此描述的是从不含二价硫离子的酸性水溶液中将硫化铑沉淀在碳上的方法。其它贵金属硫化物催化剂(如钌、铂、钯或铱的硫化物)的沉淀反应仅需要作出本领域技术人员容易得到的较小的调整。
将7.62g RhCl3·H2O溶于1升去离子水中,并将溶液回流(贵金属前体溶液的制备)。
将得自Cabot Corporation的7g Vulcan XC72-R高表面积碳黑添加至溶液中,于40℃将混合物声波处理1小时(进一步含有碳颗粒的贵金属前体溶液的制备)。
将8.64g(NH4)2S2O3在60ml去离子水中稀释,之后测定pH为7.64(含有含硫物质的水溶液的制备)。
将铑/Vulcan溶液加热至70℃,同时搅拌并监控pH。一旦达到70℃,将硫代硫酸盐溶液以4份等分试样(15ml每次)添加,每两分钟一次。在每次添加之间,检测溶液的pH的稳定、温度和颜色。
在硫代硫酸盐溶液的最后一份等分试样添加完之后,将所得溶液加热至100℃,并且保持温度1小时。通过检测颜色的变化来监控反应:初始的深粉色/橙色,其随着反应的进行逐渐变为褐色,最终由于反应完成而变为无色,这显示了产品全部吸附在碳上。在这个阶段还用醋酸铅试纸于不同的时间进行抽样检测,其证实在反应环境的任何时间不存在游离二价硫离子。使沉淀物沉降,然后过滤;用1000ml去离子水洗涤滤液以去除任何剩余反应物,然后收集滤饼,并且在110℃空气干燥过夜。
最终将干燥的产品在流动的氩气下于650℃进行1小时热处理,造成22.15%的重量损失。
首先在腐蚀测试中检测所得碳负载催化剂的性能,以检测其在盐酸电解环境中的稳定性。
为了达到这一目的,在与US 6,149,782的实施例4所公开的条件相同的情况下,将部分试样在氯饱和HCl溶液中加热至沸腾。所得溶液的颜色是硫化铑更稳定形式的特有的微粉色。
还检测了催化剂在盐酸电解中的实际性能,该催化剂按照本发明方法制备并被掺入到本领域已知的导电网上的气体扩散结构中。在由De Nora North America/USA生产的碳布基气体扩散器上以1mg/cm2的贵金属负载获得了催化剂/粘结剂层;将水悬浮液中的PTFE用作粘结剂。将这样获得的气体扩散电极在强制通风下于340℃烧结,然后将其在盐酸电解实验室电池中用作氧气-还原阴极。在两个星期的操作期间记录了在4kA/m2下持续低于1.2V的稳定的电压,这是优异电化学性能的证明。
实施例2
用同样的方法制备与前一个实施例的硫化铑催化剂等价的硫化铑催化剂,区别在于:使用连四硫酸钠取代硫代硫酸铵作为含硫物质。
将7.62g RhCl3·H2O溶于1升去离子水中,并将溶液回流(贵金属前体溶液的制备)。
将得自Cabot Corporation的7g Vulcan XC72-R高表面积碳黑添加至溶液中,于40℃将混合物声波处理1小时(进一步含有碳颗粒的贵金属前体溶液的制备)。
将17.86g Na2S4O6·2H2O在100ml去离子水中稀释,之后测定pH为7.72(含有含硫物质的水溶液的制备)。
将铑/Vulcan溶液加热至70℃,同时搅拌并监控pH。一旦达到70℃,将连四硫酸盐溶液以4份等分试样(25ml每次)添加,每两分钟一次。在每次添加之间,检测溶液的pH的稳定、温度和颜色。
在连四硫酸盐溶液的最后一份等分试样添加完之后,将所得溶液加热至沸腾并持续1小时。通过检测颜色的变化来监控反应:初始的黄色,其随着反应的进行逐渐变为褐色,最终由于反应完成而变为无色,这显示了产品全部吸附在碳上。在这个阶段还用醋酸铅试纸于不同的时间进行抽样检测,其证实在反应环境的任何时间不存在游离二价硫离子。使沉淀物沉降,然后过滤;用1000ml去离子水洗涤滤液以去除任何剩余反应物,然后收集滤饼,并且在110℃空气干燥过夜。
最终将干燥的产品在流动的氮气下于650℃进行2小时热处理,造成24.65%的重量损失。
将所得碳负载催化剂进行与前面实施例相同的腐蚀和电化学测试,显示了同样的结果。
通过使用按照已知过程、在存在本领域技术人员很容易得到的微小调节的条件下在先制备的连三硫酸钠、连四硫酸钠和连七硫酸钠前体,获得了同样的硫化铑催化剂。在这些情况下获得了类似的腐蚀和电化学结果。
实施例3
一种硫化铑-钼催化剂,其通过下面的过程制备:向500ml烧杯中加入250ml在先回流的3g/l的RhCl3·H2O溶液(约0.75g铑,相当于0.0073摩尔)。
将得自Cabot Corporation的3.37g Vulcan XC72-R高表面积碳黑添加至溶液中,于40℃将混合物声波处理1小时(进一步含有碳颗粒的贵金属前体溶液的制备)。
将1.9g四硫代钼酸盐(tetrathiomolybdate)(NH4)MoS4在70ml去离子水中稀释(含有第二金属的含硫物质的制备,在这种情况下是一种非贵金属硫代酸盐(thionate))。
将铑-Vulcan前体溶液加热至70℃,同时搅拌并监控pH。一旦达到70℃,将四硫代钼酸盐溶液以4份等分试样添加,每两分钟一次。在每次添加之间,检测溶液的pH的稳定、温度和颜色。
在四硫代钼酸盐溶液的最后一份等分试样添加完之后,将所得溶液加热至沸腾并持续1小时。通过检测颜色的变化来监控反应:初始的黄色,其随着反应的进行逐渐变为浅黄色,最终因反应完成而变为无色,这显示了产品全部吸附在碳上。在这个阶段还用醋酸铅试纸于不同的时间进行抽样检测,其证实在反应环境的任何时间不存在游离二价硫离子。使沉淀物沉降,然后过滤;用500ml温热的(80℃)去离子水洗涤滤液以去除任何剩余反应物,然后收集滤饼,并且在110℃空气干燥过夜。
实施例4
一种硫化钌-铑催化剂,其通过下面的过程制备:向500ml烧杯中,以所得约80%Ru和20%Rh的结果重量比,加入100ml在先回流的12g/l的RuCl3·H2O溶液(约1.2g Ru+3)和100ml在先回流的3g/l的RhCl3·H2O溶液(约0.75g Rh)。
用去离子水使溶液成为350ml,将得自Cabot Corporation的3.5gVulcan XC72-R高表面积碳黑添加至溶液中。于40℃将混合物声波处理1小时(进一步含有碳颗粒的两种不同贵金属前体溶液的制备)。
将4.35g(NH4)2S2O3在20ml去离子水中稀释,之后测定pH为7.64(含有含硫物质的水溶液的制备)。
将铑-钌/Vulcan溶液加热至70℃,同时搅拌并监控pH。一旦达到70℃,将硫代硫酸盐溶液以4份等分试样(每次5ml)添加,每两分钟一次。在每次添加之间,检测溶液的pH的稳定、温度和颜色。
在硫代硫酸盐溶液的最后一份等分试样添加完之后,将所得溶液加热至100℃并保温1小时。通过检测颜色的变化来监控反应:初始的深粉色/橙色,其随着反应的进行逐渐变为褐色,最终因反应完成而变为无色,这显示了产品全部吸附在碳上。在这个阶段还用醋酸铅试纸于不同的时间进行抽样检测,其证实在反应环境的任何时间不存在游离二价硫离子。使沉淀物沉降,然后过滤;用700ml温热的去离子水洗涤滤液以去除任何剩余反应物,然后收集滤饼,并且在110℃空气干燥过夜。
上述描述不应被视为对本发明的限制,其可根据不同的情况在不悖离其范围的条件下实施,并且其延伸仅仅由所附的权利要求所定义。
在本申请的说明书和权利要求中,词语“包括(comprise)”及其变形如“comprising”并不意在排除存在其它成分或附加组分的情况。
Claims (14)
1、一种制备贵金属硫化物催化剂的方法,所述方法包括:使至少一种贵金属前体的溶液与含有含硫物质的水溶液在0.1-4之间的pH下在50℃-沸腾温度的温度范围内在基本上不含硫化物的环境中反应,所述含硫物质选自硫代硫酸盐、连二硫酸盐、连三硫酸盐、连四硫酸盐、连五硫酸盐、连七硫酸盐和贵金属或非贵金属硫代酸盐。
2、权利要求1的方法,其中所述至少一种贵金属前体为氯化物。
3、权利要求1的方法,其中所述至少一种贵金属前体的溶液和所述含有含硫物质的水溶液的pH在1-4之间。
4、权利要求3的方法,其中所述至少一种贵金属前体的溶液进一步含有碳颗粒。
5、权利要求4的方法,其中所述碳颗粒为表面积超过50m2/g的碳黑。
6、权利要求1的方法,其中所述含硫物质为钠盐或铵盐形式。
7、权利要求3的方法,其中所述含硫物质为钠盐或铵盐形式。
8、权利要求4的方法,其中所述含硫物质为钠盐或铵盐形式。
9、权利要求1的方法,其中将所述含有含硫物质的水溶液以不连续的等分试样,以15秒-10分钟的时间间隔添加到所述贵金属前体的溶液中。
10、权利要求1-9任一项的方法,其中将所述含有含硫物质的水溶液添加到所述至少一种贵金属前体溶液中,并且使所得溶液处于沸点温度5-120分钟,直到反应完成。
11、权利要求10的方法,其中所述反应的完成通过检测颜色变化而确定。
12、权利要求10的方法,所述方法进一步包括分离所得贵金属硫化物催化剂,并将其在150-700℃之间的温度下进行热处理。
13、权利要求1-9任一项的方法,其中所述至少一种贵金属选自钌、铑、铂、铱和钯。
14、权利要求10的方法,其中所述至少一种贵金属选自钌、铑、铂、铱和钯。
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CN108823602B (zh) * | 2018-07-12 | 2021-01-15 | 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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GB1066579A (en) * | 1963-11-12 | 1967-04-26 | Engelhard Ind Inc | Catalyst |
EP0289211A1 (en) * | 1987-04-22 | 1988-11-02 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating hydrocarbons and method of activating the same |
EP0898318A2 (en) * | 1997-08-01 | 1999-02-24 | Matsushita Electric Industrial Co., Ltd. | Method for producing electrode catalyst powder |
US6149782A (en) * | 1999-05-27 | 2000-11-21 | De Nora S.P.A | Rhodium electrocatalyst and method of preparation |
CN1362493A (zh) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | 一种重质油加氢处理催化剂的硫化方法 |
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2005
- 2005-01-25 ZA ZA200605826A patent/ZA200605826B/xx unknown
- 2005-01-25 CN CNB2005800035175A patent/CN100428988C/zh active Active
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1066579A (en) * | 1963-11-12 | 1967-04-26 | Engelhard Ind Inc | Catalyst |
EP0289211A1 (en) * | 1987-04-22 | 1988-11-02 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating hydrocarbons and method of activating the same |
EP0898318A2 (en) * | 1997-08-01 | 1999-02-24 | Matsushita Electric Industrial Co., Ltd. | Method for producing electrode catalyst powder |
US6149782A (en) * | 1999-05-27 | 2000-11-21 | De Nora S.P.A | Rhodium electrocatalyst and method of preparation |
CN1362493A (zh) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | 一种重质油加氢处理催化剂的硫化方法 |
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ZA200605826B (en) | 2009-06-24 |
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