CN1957112B - 用于氧气析出的阳极 - Google Patents

用于氧气析出的阳极 Download PDF

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CN1957112B
CN1957112B CN2005800161445A CN200580016144A CN1957112B CN 1957112 B CN1957112 B CN 1957112B CN 2005800161445 A CN2005800161445 A CN 2005800161445A CN 200580016144 A CN200580016144 A CN 200580016144A CN 1957112 B CN1957112 B CN 1957112B
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P·罗西
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Abstract

一种用于高过电压氧气阳极析出的电极，包括钛或其它阀金属基材、包含阀金属氧化物的第一保护中间层、包含铂或其它贵金属的第二中间层以及包含锡、铜和锑的氧化物的外层。本发明的电极可以在废水处理中用作阳极。

Description

用于氧气析出的阳极
本发明涉及用于在水溶液中高过电压氧气析出(evolution)，例如用于破坏废水中的有机物的阳极。在通常的水处理中，以及特别是在当必须将有机或生物物质减少到非常低水平时的废水处理中，氧气的阳极析出是一种非常常用的反应。在破坏有机物质中，初生氧的有效性主要取决于阳极析出电位，其必须尽可能的高，优选不需要使用过量的电流密度。其它工业过程，例如有机电合成领域可以得益于在本发明的阳极上以高电位析出氧气，尽管如此氧化水溶液中有机物质无疑代表其最普遍和经济学上相关的用途。
现有技术中用于高过电压氧气析出的阳极通常在例如基于用其它元素不同改性的二氧化锡的陶瓷基材上获得，主要是为了赋予充足的导电性；二氧化铅也代表通常用于该目的的材料。但是这种基材类型的几何局限性已经促使研发基于阀金属的具有高氧气过电压的电极，其具有优选的结构，包括钛或钛合金基材、例如基于氧化钛和氧化钽的保护陶瓷中间层以及其中二氧化锡同样代表主要组分，通常与其它元素，例如铜、铱和锑成混合物的低催化活性外层；这种电极也包括主要含有氧化钽和氧化铱的中间催化剂层，公开于WO03/100135的实施例6中。虽然WO03/100135的电极能够在指明的应用中提供有吸引力的初始性能，但是由于其在含硫溶液中以略微高于2V的电位和100A/m2的电流析出氧气，其寿命相当不令人满意。实际上，即使以上阳极装备有低催化活性外层，在普通工业操作条件中，氧气析出电位和有机物质去除效率也倾向于在几百小时内突然下降。另外，从WO03/100135的说明书中可以很快注意到有关电极的制备方法对于大规模生产来说相当复杂，因为必须应用两种不同前体的大量替代层(在实施例中，每两个涂层十个替代层)。
本发明的一个目的是提供一种氧气析出阳极，其在不超过几百A/m2的电流密度下，在高于2V(NHB)的高过电压下工作，克服了现有技术的局限同时在工业工作条件中提供更长的寿命。
本发明的另一个目的是提供一种生产高过电压氧气析出阳极的方法，特征在于便利的工业实用性。
在第一方面，本发明包括一种在陶瓷基材上或者优选在钛、钛合金或其它阀金属基材上得到的阳极，所述阳极包括基于本领域已知的阀金属氧化物的第一保护中间层，基于贵金属的第二保护中间层和包含锡、铜和锑氧化物的外层。
在一个优选的实施方案中，根据本发明活化的钛或钛合金基材预先例如通过喷砂以及后续的硫酸蚀刻具有合适的粗糙外观。
在另一个优选的实施方案中，第一中间层包括钛和钽氧化物的混合物；在另一个优选的实施方案中，基于贵金属的第二中间层包含铂，更优选包含10-24g/m2的铂。
外层包含锡、铜和锑氧化物，任选与其它元素结合。锡含量优选为5-25g/m2，锑含量为0.4-2g/m2，铜含量为0.2-1g/m2；在一个更加优选的实施方案中，锡以全部金属含量的至少90重量％的量存在。
在另一个方面，本发明包括一种生产高过电压氧气析出阳极的方法，所述方法包括在陶瓷或阀金属基材上后续施加基于阀金属氧化物的第一保护中间层，基于贵金属的第二中间层和包含锡、铜和锑氧化物的外层。在一个优选的实施方案中，基材为例如通过喷砂接着通过硫酸蚀刻预先加以处理，以便赋予适合的粗糙外观的钛或钛合金，如03/076693中公开的。但是可能进行其它类型的处理，例如热或等离子体喷涂处理或用其它腐蚀剂蚀刻。在一个优选的实施方案中，第一中间层通过施加前体，例如钛和钽氯化物，然后在例如450-600℃之间进行热分解得到；如本领域已知的，该前体施加可以由例如喷涂、刷涂或辊涂的不同的单一或组合技术实施。在一个优选的实施方案中，第二中间层通过在400-600℃温度下热分解六氯铂酸得到，但是也可以进行其它形式的贵金属施加，例如通过电化步骤。在形成第二中间层的过程中，可以包括其它贵金属的前体，但是特别优选存在铂。
在一个特别优选的实施方案中，使用含有锡、铜和锑氧化物的前体，例如相应的氯化物的单一溶液施加外层。溶液根据现有技术施加，并且优选在450-600℃之间分解。
本发明的阳极能够在几百A/m2的电流密度下，在电位明显高于2V(NHE)的高过电压下析出氧气，比WO03/100135的阳极或者现有技术的其它阳极具有长得多的寿命。不希望本发明束缚于特定理论，就WO03/100135而论，假定阳极倾向于在涂布中形成裂纹或裂缝，虽然其使有限扩展的一些区域剥离，但是具有高铱含量或者在任何情况下具有明显较低的氧气过电压。就本发明的阳极而论，可能形成的裂纹或裂缝将使富铂区域剥离，在其上氧气过电压仍然相当高。
这种说明由附图中公开的数据证实。
图1显示与本发明阳极上的氧气析出相应的极化曲线。
特别地，图1中的曲线表示在pH5和25℃下硫酸钠中的氧气析出。
(1)表示与本发明阳极相应的极化曲线，(2)表示与仅具有分别基于钛和钽氧化物以及基于铂的两个中间层的本发明阳极的极化曲线，(3)表示与仅具有基于钛和钽氧化物的第一中间层和基于铱和钽氧化物的外层的阳极的极化曲线。实际上，曲线(2)模拟其中基于锡、铜和锑氧化物的外层完全破坏的本发明阳极的行为，而曲线(3)模拟WO03/100135的阳极的最外层全部破坏的情况。
本发明将进一步由以下实施例阐明，并不希望本发明的范围限于以下实施例，而是仅由附加的权利要求加以限定。
实施例
在87℃温度下，用金刚砂喷砂以及用含有10g/l溶解钛的25％硫酸蚀刻45cm×60cm尺寸和2mm厚度的根据ASTM B265的1级钛板。通过静电喷涂，接着辊涂将溶液施加于以0.11M Ti和0.03M Ta的浓度含有钛和钽氯化物的片材上。施涂四层溶液涂层，直到得到0.87g/m2的沉积总载荷，在50℃下在一个涂层和下一个涂层之间干燥10分钟，以及随后在520℃热分解15分钟。
由此得到第一中间层，在其上施涂包括20g/m2Pt的第二中间层。通过刷涂分散在丁香酚中的六氯铂酸，以及通过在每个涂布之后在500℃热分解10分钟，以三个涂层进行施涂。
最后施涂来源于锡(IV)(相当于全部金属含量的94重量％)、铜(II)(相当于全部金属含量的2重量％)和锑(相当于全部金属含量的4重量％)氯化物的外层。通过刷涂16层涂层，使用在每个涂层之后在50℃干燥和在520℃分解，进行施涂。
在pH5和25℃下根据硫酸钠中的氧气析出对由此得到的本发明电极进行极化测试，以及结果公开在图1中的作为(1)标明的曲线。图1中也公开了以相同条件用不含外层的相同电极，和用装备有相同第一中间层的电极，以及用含有24g/m2的钽(35重量％)和铱(65重量％)氧化物的外层得到的极化数据。这种数据公开在分别作为(2)和(3)标明的曲线中。
最后，对本发明电极进行加速寿命测试，其中该测试在60℃和20kA/m2的电流密度下，在浓度为150g/l的硫酸中的氧气析出下进行。加速测试500小时之后，在500A/m2电流密度测量pH5和25℃下硫酸钠中的氧气析出电位：得到的测定电位等于2.15V(NHE)。对根据WO03/100135制备的阳极进行相同测试，在相同条件下显示1.74V(NHE)的氧气析出电位。
对于本领域技术人员显而易见的是，本发明可以相对于列举的实施例实际进行其它变化或改进。
前述说明书目的并不在于限制本发明，本发明可以根据不脱离其范围的不同实施方案加以应用，并且其范围仅由附加的权利要求唯一限定。
贯穿本申请的说明书和权利要求，措词“包括”及其变化，例如“包含”和“含有”并不用来排除存在其它元素或附加组分。

Claims (15)

1.用于高过电压氧气析出的阳极，包含阀金属或陶瓷基材，施加于所述基材的基于阀金属氧化物的第一中间层，施加于所述第一中间层的铂中间层，含有锡、铜和锑的氧化物的外层。
2.权利要求1所述的阳极，其中所述阀金属基材由钛或钛合金制成。
3.权利要求2所述的阳极，其中所述钛或钛合金的基材具有粗糙外观，该粗糙外观通过包括任选在先进行喷砂的硫酸蚀刻的处理加以控制。
4.权利要求1所述的阳极，其中所述第一中间层包括钛和钽氧化物。
5.权利要求1所述的阳极，其中所述铂中间层包括10-24g/m2的铂。
6.前述权利要求中任一项所述的阳极，其中所述外层包括5-25g/m2的锡，0.4-2g/m2的锑和0.2-1g/m2的铜。
7.权利要求6所述的阳极，其中锡以不低于全部金属含量的90重量％的量存在于所述外层中。
8.生产用于高过电压氧气析出的阳极的方法，包括向阀金属或陶瓷基材施涂基于阀金属氧化物的第一中间层，向所述第一中间层施涂铂中间层，以及施涂含有锡、铜和锑的氧化物的外层。
9.权利要求8所述的方法，其中所述基材为钛或钛合金基材，具有通过喷砂以及后续硫酸蚀刻得到的受控的粗糙外观。
10.权利要求8或9所述的方法，其中所述第一中间层通过选自喷涂、刷涂和辊涂的至少一种方法，由来自钛和钽的氯化物的溶液开始，以及随后在450-600℃下热分解进行施加。
11.权利要求8或9所述的方法，其中所述铂中间层通过在400-600℃之间热分解含有六氯铂酸的溶液进行施加。
12.权利要求8或9所述的方法，其中所述外层由来自含有锡、锑和铜的氯化物的溶液开始，以及随后在450-600℃下热分解以多层涂层进行施加。
13.电化学方法，包括在权利要求1-7中任一项所述的阳极上以高于2V/NHE的电位进行阳极氧气析出。
14.权利要求13所述的方法，包括工业水处理。
15.权利要求14所述的方法，其中所述处理包括从废水中除去有机分子。
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