CN103153447B - 用于沉积薄的选择性膜层的新的种晶方法 - Google Patents

用于沉积薄的选择性膜层的新的种晶方法 Download PDF

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CN103153447B
CN103153447B CN201180042241.7A CN201180042241A CN103153447B CN 103153447 B CN103153447 B CN 103153447B CN 201180042241 A CN201180042241 A CN 201180042241A CN 103153447 B CN103153447 B CN 103153447B
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transition metal
film
carrier
layer
palladium
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CN103153447A (zh
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L·A·科雷亚
J·P·奥弗贝克
Y·C·范德尔夫特
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Abstract

提供一种在多孔载体上制造过渡金属基的膜或其它层的方法。所述层适合用于氢气分离、氧气分离、或者保护或装饰目的，其通过以下步骤制备：通过用过渡金属盐溶液进行涂布而预处理所述多孔载体，干燥该经种晶的载体，将所述过渡金属盐还原为过渡金属，和用含有过渡金属(钯、银或其它金属)和任选存在的其它金属的配合物来进行化学镀。所述膜可为其外侧有1-10μm的过渡金属层的管状物。

Description

用于沉积薄的选择性膜层的新的种晶方法
技术领域
本发明涉及制造用于分离氢气的过渡金属基的层和膜的方法，并涉及由该方法获得的膜。
背景技术
具有多孔载体和薄的致密钯层的非对称膜可用于将氢气与其它气体分离，所述气体例如二氧化碳及其它小分子气体(如烃类和其它氢化物)。比较经济的通过对多孔载体进行化学镀而制造钯基膜的方法要求在所述多孔载体上存在钯晶种。为了生长基本上没有缺陷的薄的致密Pd膜，在载体上应均匀分布足够数量的晶种。
包含多孔载体和薄的致密银层的非对称膜可用于将氧气与其它小分子分离(见例如http://www.anorg.chem.uu.nl/PDF/Bergwerff_silver％20literature.pdf)。
Collins和Way(Ind.Eng.Chem.Res.1993，32，3006-13)使用氯化锡多次预处理载体，随后在用钯-胺配合物反复化学镀之前对其进行酸性氯化钯浸渍。Li等人(CatalysisToday，56，2000，45-51)类似地使用氯化锡预处理，随后在强化化学镀之前用用由渗透驱使的酸性钯胺预处理。Paglieri等人(Ind.Eng.Chem.Res.1999，38，1925-1936)提出一种改进的种晶方法，其中将载体内部浸渍在醋酸钯溶液(其中使用氯仿作为溶剂)中，随后干燥和焙烧。所得膜的厚度为～20μm，并且其H2/N2选择性不高于50。Zhao等人(CatalysisToday，56，2000，89-96)使用一种活化方法，其中用Pd-改性的勃姆石溶胶进行粉浆浇铸，随后干燥和焙烧。CN1164436和US2008-176060也描述了使用勃姆石溶胶。KR2001-045207和KR2001-018853描述了用硅溶胶预处理。Hou等人(WO2005/065806)在氯化锡处理之后种晶之前使用勃姆石溶胶作为孔填充剂。焙烧之后，在孔中形成γ-氧化铝，从而修复了载体的多孔结构。Harold等人(US2008/0176060)用两层γ-氧化铝层将通过化学镀施加的钯晶种(层)夹在中间，从而所述晶种充当用于在也是通过化学镀生成的顶部γ-氧化铝层的孔中生长钯的核。
这些现有方法导致这样所获得的膜的氢气通量、H2/N2选择性和稳定性等性能不足。氯化锡预处理导致存在锡污染，这既影响了镀敷浴的稳定性又影响了钯膜的温度稳定性。即使当预处理不含锡盐预处理时，如Paglieri仅使用醋酸钯的改进方法，所获得的膜较厚且其具有50的低选择性而使人失望。在制造时使用氯仿作为溶剂是这些方法中的另一个缺陷。使用勃姆石溶胶及类似物可能导致孔堵塞并因此降低分离性能。由于热稳定性有限，还可能降低最高使用温度。而且，现有方法不总是能够制造非常薄的钯层。
因此本发明的目的是提供一种基于钯的薄膜的制造方法，该方法提高了钯基分离层的性能，并能够制造具有非常薄(＜5μm)的钯层的分离膜。
发明内容
本发明涉及一种制造过渡金属基的层的方法，所述层可适合于气体分离、装饰或抗菌目的、防腐蚀、或其它目的，所述方法包括：
-用过渡金属盐的溶液预处理多孔载体，
-干燥该载体，
-将所述过渡金属盐还原为相应的过渡金属，
-用一种或多种过渡金属配合物进行化学镀。
特别地，所述层为多孔载体上膜的一部分。
优选地，本发明的方法不包括用锡盐进行预处理。而且，不优选用其它的非过渡金属化合物预处理所述载体。此外，优选避免使用可能有害的溶剂，例如对于钯盐而言所述可能有害的溶剂为氯烷烃。
本发明还涉及多孔载体上过渡金属基的膜，该膜适合用于气体分离，所述膜的特征在于一侧的过渡金属层的厚度在1-10μm之间。
具体实施方式
本发明的层或膜通过厚度最大5μm并且不小于0.5μm的过渡金属晶种与多孔载体固定(anchor)。由于表面平滑减少了表面上污染物的累积，过渡金属膜具有有光泽的外观。
多孔载体优选为圆柱几何体，例如管，尤其用于分离目的；但其也可以是平的，或具有任何其它的形状，例如用于装饰应用。载体可为任何陶瓷材料，例如氧化铝、氧化锆、二氧化硅；金属，例如铸铁、不锈钢；或有机聚合物，例如聚乙烯、聚丙烯，等等。如果载体为圆柱几何体，则载体中沿着轴线的通道数量可为1或更大，优选6n+1(n是整数，优选1-10，更优选1-7，最优选1或3)，以六角形、拟圆柱形布置，更优选1、7(2+3+2)、19(3+4+5+4+3)、或43(1+4+7+6+7+6+7+4+1)个通道，最优选7、19。管可具有任意长度，所述长度可由几个因素确定，例如可利用的热处理设备和预定的用途。优选长度为0.4-5米。最优选长度在0.5和2米之间，例如约1米。载体的孔隙率和孔径大小不是关键的，只要孔宽得足以使处理溶液能足够渗透。优选地，孔径为至少25nm。更优选，载体为孔径大小在50nm-1μm范围内、最优选在100-500nm范围内的大孔载体。
在本发明方法的一个优选实施方案中，将过渡金属层施加在管状多孔载体的外侧上，从而得到具有外过渡金属层的膜，因而与该选择性层位于管内部的情况相比，在分离过程中能够使用较高的进料压力。
在另一个优选实施方案中，使用例如具有7、19或43个通道的多通道载体，因为通常它们可以更好地抵抗较高的进料压力。为了使用较高的比表面积，将过渡金属层施加在单个通道的内部。
在本说明书中，过渡金属是选自元素周期系中4-6周期的3-12族(Ⅲb-Ⅱb)(元素序数21-30、39-48和57-80)的元素，尤其是选自4-11族(Ⅳb-Ⅰb)的元素。特别地，过渡金属为选自铂族(8-10族或Ⅷb)或金族(11族或Ⅰb)的元素。预处理步骤优选使用选自铂族(Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt)的一种或多种金属进行，而通过化学镀施加的最后的金属层优选为包含选自10和11族(Ni、Cu、Pd、Ag、Pt、Aa)和Rh、Ru、Cr的一种或多种金属的层，最优选包含至少40％(w/w)的钯(Pd)和/或银(Ag)、和/或镍(Ni)的层。
预处理
在本发明的方法中，用于预处理溶液中的过渡金属盐是可溶性的，尤其水溶性的，优选二价的过渡金属盐，例如氯化钯、硝酸钯、硫酸钯或硒酸钯、氯化铂、硝酸铂、铑(Ⅲ)氯化物、氯化镍、硝酸镍、硫酸镍等等。这些盐与例如醋酸盐相比得到更均匀的覆盖结果。同样为了均匀覆盖，优选的盐是铂(Ⅳ)氯化物和钯(Ⅱ)氯化物。过渡金属盐溶液的浓度可为例如56-225mM，优选113-188mM。这些值相当于例如6-24g之间、优选12-20gPd每升，或11-43.9g之间、优选22-36.7gPt每升，或3.3-13.2g之间、优选6.6-11.0gNi每升，对于其它金属也是类似。
优选的溶剂是便宜的且无危险的，并对过渡金属盐有高溶解度。优选的溶剂包括水、低级醇(例如2-丙醇)和丙酮；最优选的过渡金属盐溶液是含水溶液，“含水”表示超过50％(按重量计)的溶剂由水组成。最优选的溶剂是水。不优选使用氯仿。而且，不优选其它的卤代烷。可利用任何涂布技术进行处理，例如浸涂、喷涂、刷涂等等。有利的涂布方法是膜涂布，其可以容易地控制浸渗深度和负荷量。
按照使过渡金属盐溶液充分地渗透进入载体而不过量渗透的方式选择预处理条件。这可以通过使用相对短的接触时间来实现，例如采用膜涂布法。优选钯的渗透深度在1-10μm之间，更优选不超过5μm。优选对溶液的量和浓度以及接触时间进行选择，从而使得进入孔的过渡金属(钯、铂或其它金属)还原之后的量在5-15mg每100mm管长度的范围内。因此优选的涂布速率在5-100mm/s之间，优选在15-75mm/s之间，最优选在25-60mm/s之间。
预处理优选使经预处理的载体中过渡金属的量在10-30mg、优选12-24mg每10,000mm2(dm2)之间。当载体是管状物、尤其是外直径在12和18mm之间的管状物时，过渡金属的量优选为5-12mg每100mm管长度。通过改变预处理溶液中过渡金属的浓度可进一步调节负荷量和渗透深度。例如可利用扫描电子显微镜(SEM)光测法来检查负荷量和渗透深度。
多孔载体可任选由致密支撑体支撑，并可用作粗糙的固定层。支撑体优选在预处理之前具有足够的可润湿性。如果必要，可润湿性可通过使用适当的蚀刻剂——例如氢卤酸——进行等离子体(化学)蚀刻而改善。
预处理可以是单个涂布步骤，或反复的涂布步骤，所述反复的涂布步骤具有间歇的局部或完全干燥。预处理之后，将经预处理的载体在环境温度或升高的温度下干燥，例如在40和100℃之间的温度下干燥。
还原
下一步骤是通过将过渡金属还原为零价态来活化该过渡金属。优选通过用含氢气的气体或其它的还原气体在升高的温度下处理而实现。含氢气的气体可以是例如纯氢，也可是由氢气和其它惰性气体(例如氩气或氮气)、或另一种还原气体构成的混合物。还原步骤的有利条件包括温度在400-700℃之间，优选在475-625℃之间。随后将承载经还原的过渡金属(钯、铂或其它金属)晶种的膜在惰性气氛(例如氮气)下冷却至环境温度。
镀敷
最后将钯和/或其它金属沉积在经过渡金属种晶的载体上，例如采用化学镀的方法，根据使用以下物质的本身已知的化学镀(即自催化镀敷)的方法：过渡金属配合物，例如四-氨钯二氯化物(Pd(NH3)4Cl2.2H2O)、六氯铂酸铵、二氨银盐、五氯钌酸钾、及其组合；稳定剂，例如EDTA；和还原剂，例如肼。例如Collins和Way(Ind.Eng.Chem.Res.1993)和以上在“背景技术”部分中所引用的其它参考文献描述了化学镀的方法。本发明预处理的结果为，增加了化学镀镀敷浴的稳定性，例如只有不均匀的沉淀而没有均匀沉淀。这表示只有过渡金属形成在载体的表面上，而在镀敷浴自身内没有形成结晶物质。结晶物质的均匀沉淀会产生混浊的溶液，从而使得在载体上和镀敷浴底部上沉积不规则的凝集材料，并因此消耗过渡金属前体和降低镀覆速率。可在“ElectrolessPlating，FundamentalsandApplications”，Ed.O.Mallory&Hajdu，AmericanElectroplatersandSurfaceFinishersSociety，Inc.NoyesPublications，NY中找到关于包括镍、银、铜、金、铂、钴等过渡金属的化学镀的详细描述。
代替钯，或特别是除了钯，可使用其它的适当金属，例如银、铂、铜、金、铑、钌和铬。因此，在上下文中每次提及“钯”时，其可全部、或优选部分(合金)被其它的金属替换，所述其它的金属特别是镍、铜、银和/或金。本发明的膜中，金属层优选包含5-95wt.％的一种或多种金属，其选自镍、钯、铂、铜、银、铑和金。
优选镀敷层中的钯含量为至少40wt.％，更优选至少50wt.％。特别有利的是含50-95wt.％的钯和5-50wt.％的其它金属的合金。这些其它金属，除了包含磷(特别是与镍结合的磷)，还包含选自8-11族(Ⅷ和Ⅰb)——例如镍、铜、钌、铑、铂、银和金——和诸如钇、铈、铟、铬、锆等金属的一种或多种金属。包含65-85wt.％的钯和15-35wt.％的银的钯合金是特别有用的。而且，包含70-99wt.％的钯和1-30wt.％的铜和/或金的合金非常适合用于氢气分离。
或者，膜层可包含至少40wt.％、更优选至少50wt.％的银和/或镍，特别是银。包含65-85wt.％的银和5-35wt.％锆、以及任选存在的0-25wt.％的其它金属的合金是特别有用的。钯、铂、银或其它合金的化学镀可利用含有有关金属盐的镀敷浴进行，所述有关金属盐例如以需要比例由氯化钯或硝酸钯和硝酸银构成的混合物。
当制造合金层时，首先实施第一金属(例如钯或银)镀敷步骤、然后可用第二镀敷浴施用其它的一种或多种金属，这样是有利的。在所述多步合金制造中，优选所述第二镀敷浴和任选存在的其它镀敷浴包含一些(例如在2-20wt.％之间)钯以促进镀敷过程。
应用
可由上述方法制造的在多孔载体上的过渡金属基的膜特别适合于氢气分离。该膜特征在于一侧的过渡金属层的厚度在1-10μm之间。优选，过渡金属层的厚度在2至5μm之间，最优选在2-4μm之间。优选，过渡金属层包含40-100wt.％的钯、更优选50-95wt.％的钯，和0-60wt.％、更优选5-50wt.％、最优选10-40wt.％的如上述的其它金属，特别是镍、铂、铜、银和/或金。
如上所述，膜的优选实施方案是管状膜，更优选外表面有过渡金属层的管状膜。特别地，管状膜的外直径在5-50mm之间，优选在10-25mm之间。氢气渗透度为至少5.10-7mol/m2.s.Pa，特别是至少10-6mol/m2.s.Pa，或甚至至少2.10-6mol/m2.s.Pa。H2/N2选择性，即氢气相对于氮气的相对透过率，为至少200、特别是至少1000、或甚至至少5000。
本发明还涉及一种从气体混合物中分离氢气的方法，所述方法包括使所述气体混合物通过如上所述的膜。所述膜将选择性地使氢气通过并从而将其与其它气体分子分离，所述其它气体分子包含：氧化物，例如一氧化碳、二氧化碳、和氮氧化物；和氢化物，例如氨、水、烃类(甲烷、乙烷、乙烯、和高级同系物)。由于本发明方法制造的薄膜没有缺陷，可用本发明方法获得的膜具有以下优点：其具有较低的厚度并因而具有较高的渗透度，从而提供较高的选择性(更好的分离)。
或者，所述过渡金属层包含40-100wt.％的银、更优选50-95wt.％的银，和0-60wt.％、更优选5-50wt.％、最优选10-40wt.％的如上所述的其它金属，特别是镍、铂、钯、铜、金和/或锆或其它的贱金属(lessnoblemetal)。
因此，在另一个实施方案中，本发明涉及一种从气体混合物中分离氧气的方法，所述方法包括使所述气体混合物通过如上所述的膜。所述含银的膜将选择性地使氧气通过并从而将其与其它气体分子分离。由于本发明方法制造的薄膜没有缺陷，可用本发明方法获得的膜具有以下优点：其具有较低的厚度并因而具有较高的渗透度，从而提供较高的选择性(更好的分离)。
在又一个实施方案中，本发明涉及用于抗菌、保护、装饰或其它的目的除了膜之外的层，所述层包含过渡金属，尤其贵金属或准贵金属(pseudonoblemetal)，例如银、金、钯、铬等等。例如，已知非常薄的金层(100nm)可增强镍材料的硬铜焊和焊锡。另外，珠宝也可以采用类似的方式处理。自催化沉积的镍磷合金，与电沉积的镍相比，更硬并能提供更好的保护。对于这些层的长期性能而言，载体上的固定是重要的。在杀菌剂方面，采用化学镀技术沉积的银膜是已知的(Sabbani等人，MicroporousandMesoporousMaterials，135(2010)131-136)。由于金属铑具有亮白色外观，铑最终加工经常被用于珠宝中。可通过用三氨合三(亚硝酸-N，N，N)铑(Ⅲ)进行化学镀以完成制备(US6,455,175)。
实施例
实施例1
将具有两个α-氧化铝层的500mm管状非对称的大孔Al2O3载体(外直径14mm，孔径0.2μm)用含有1.57gPdCl2、1.025mlHCl37％和63.150mlMQ水的溶液进行膜涂布。涂布速率是40mm/sec。重复一次膜涂布过程。将经涂步的管在70℃干燥。
然后将经干燥的经Pd-种晶的管通过首先在平缓流动的氮气流中慢慢地加热到500℃、然后在500℃下用氢气处理而活化。称该管的重量以确定钯晶种的负荷量。Pd负荷量为至少7mg每100mm载体。
随后将经钯-种晶的管状膜通过化学镀在55℃镀敷2小时，其中所使用的镀敷浴溶液含有5.4g/lPdCl2、70g/lEDTA(Titriplex)、434ml/lNH4OH(25w/o)和7.5ml肼(2.05M)每升镀敷浴溶液。
所得膜的厚度小于4μm，且其具有高H2/N2选择性：所述膜是不漏的，因为在该膜两侧的压差为2bar时没有测量到氮气流，并且氢气通量(渗透度)为9.5*10-7mol/m2.s.Pa。通过分别测量纯氢和纯氮的透过率而进行测量，H2/N2渗透选择性在350℃时＞1000。
实施例2
将具有一个氧化铝层和一个氧化锆层的500mm管状非对称的大孔Al2O3-ZrO2载体(外直径14mm，孔径0.2μm)用钯进行膜涂布并随后如实施例1中所述的进行活化。钯晶种负荷量为至少7mg每100mm管长度。
随后将该经钯-种晶的管状膜通过如实施例1所述的化学镀进行镀敷。所得膜的厚度小于4μm，其具有高H2/N2选择性并且是不漏的。H2/N2渗透选择性＞1000，并且氢气通量(渗透度)在350℃时为1.5*10-6mol/m2.s.Pa。
实施例3
将具有一个氧化铝层和一个氧化锆层的500mm管状非对称的大孔Al2O3-ZrO2载体(外直径14mm，孔径0.2μm)用钯进行膜涂布并随后如实施例1中所述的进行活化。钯晶种负荷量为至少7mg每100mm管长度。
随后将经钯-种晶的管状膜通过化学镀在55℃镀敷6小时，其中所使用的镀敷浴溶液含有4.8g/lAgCl2、33g/lEDTA(Titriplex)、730ml/lNH4OH(25w/o)和3.5ml肼(2.05M)每升镀敷浴溶液。
所得膜的厚度小于5μm，且其具有高O2/N2选择性：所述膜是不漏的，因为在所述膜两侧的压差为2bar时没有测量到氮气流，并且氧气通量(渗透度)＞10-8mol/m2.s.Pa。通过分别测量纯氧和纯氮的透过率而进行测量，O2/N2渗透选择性350℃时＞10。
实施例4
将具有两个α-氧化铝层的500mm管状非对称的大孔Al2O3载体(外直径14mm，孔径0.2μm)用含有1.57gPtCl4和63.150mlMQ水的溶液进行膜涂布。涂布速率是40mm/sec。重复一次膜涂布过程。将所述经涂布的管在70℃干燥。
然后将经干燥的经Pt-种晶的管通过首先在平缓流动的氮气流中慢慢地加热到500℃、然后在500℃下用氢气处理而活化。称该管的重量以确定铂晶种负荷量。Pt负荷量为至少7mg每100mm载体。
随后将该经铂-种晶的管状膜通过化学镀如实施例1所述的进行镀敷。所得膜的厚度小于4μm，其具有高H2/N2选择性并且是不漏的。H2/N2渗透选择性＞1000，并且氢气通量(渗透度)350℃时为1*10-6mol/m2.s.Pa。

Claims (24)

1.在多孔载体上制造一种或多种过渡金属的层的方法，包括：
-通过用过渡金属盐的溶液进行膜涂布而预处理所述多孔载体，其中涂布速率在5-100mm/s之间，所述过渡金属盐为选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的过渡金属的氯化物、硝酸盐、硫酸盐或硒酸盐，
-干燥该经预处理过的载体，
-将所述过渡金属盐还原为相应的过渡金属，
-用一种或多种过渡金属对所述经预处理过的载体进行化学镀。
2.根据权利要求1的方法，其中所述过渡金属盐是氯化物或硝酸盐。
3.根据权利要求2的方法，其中所述过渡金属盐是镍、钯或铂的氯化物。
4.根据权利要求1-3中任一项的方法，其中所述过渡金属盐的溶液是含水溶液，并且所述经预处理的载体的干燥在40至100℃的温度下进行。
5.根据权利要求1-3中任一项的方法，其中对所述过渡金属盐的还原用含氢的气体在400-700℃之间的温度下进行。
6.根据权利要求5的方法，其中对所述过渡金属盐的还原在475-625℃之间的温度下进行。
7.根据权利要求1-3中任一项的方法，其中所述载体是管状的并且所述经预处理过的载体中过渡金属的量在5-12mg每100mm管长度的范围内。
8.根据权利要求1-3中任一项的方法，其中所述载体是管状的并且涂布速率在15-75mm管长度每秒之间。
9.根据权利要求1-3中任一项的方法，其中进入所述载体的所述选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的过渡金属的渗透深度不超过5μm。
10.根据权利要求1-3中任一项的方法，其中所述过渡金属盐的溶液中所述过渡金属的浓度在113-188mM之间。
11.根据权利要求1-3中任一项的方法，其中用于化学镀的过渡金属选自钯、镍和银。
12.根据权利要求11的方法，其中所述过渡金属包含至少40重量％的钯。
13.多孔管状载体上基于过渡金属的管状膜，所述膜的特征在于所述载体一侧的一种或多种选自Pd、Rh、Ru、Pt、Ni、Cu、Ag、Au和Cr的过渡金属的层的厚度在1-5μm之间，并且选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的过渡金属的晶种渗透进入载体中的深度为0.5μm至5μm，所述膜的氢气相对于氮气的选择性为至少200。
14.根据权利要求13的膜，其中所述过渡金属层存在于所述管状膜的外表面。
15.多个6n+1多孔管状载体上基于过渡金属的多通道管状膜，其中n是1-10的整数，所述膜的特征在于所述管状载体内表面的一种或多种选自Pd、Rh、Ru、Pt、Ni、Cu、Ag、Au和Cr的过渡金属的层的厚度在1-5μm之间，并且选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的过渡金属的晶种渗透进入载体中的深度为0.5μm至5μm。
16.根据权利要求15的膜，其氢气相对于氮气的选择性为至少200。
17.根据权利要求13-16中任一项的膜，其氢气相对于氮气的选择性为至少1000。
18.根据权利要求13-16中任一项的膜，其中所述过渡金属层的厚度在2-5μm之间。
19.根据权利要求13-16中任一项的膜，其中所述层包含5-95重量％的一种或多种选自镍、钯、铂、铜、银、铑和金的金属。
20.根据权利要求13-16中任一项的膜，其氢气渗透度为至少5·10-7mol/m2·s·Pa。
21.多孔管状载体上基于过渡金属的管状膜，所述膜的特征在于所述载体一侧的一种或多种过渡金属的层包含至少40重量％的银和/或镍，所述层的厚度为1-5μm，选自Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt的第二过渡金属的晶种渗透进入载体中的深度为0.5μm至5μm，并且所述膜的氧气相对于氮气的选择性为至少10。
22.根据权利要求21的膜，其中所述过渡金属层存在于所述管状膜的外表面。
23.从气体混合物中分离氢气的方法，包括使所述气体混合物通过根据权利要求13-16中任一项的膜或通过由权利要求1-12中任一项的方法获得的膜，其中所述过渡金属层包含至少40重量％的钯和/或镍。
24.从气体混合物中分离氧气的方法，包括使所述气体混合物通过根据权利要求21-22中任一项的膜或通过由权利要求1-12中任一项的方法获得的膜，其中所述过渡金属层包含至少40重量％的银。
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