CN103635259B - 催化活性的、金属化的反应性泡沫材料的制备及其应用 - Google Patents

催化活性的、金属化的反应性泡沫材料的制备及其应用 Download PDF

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CN103635259B
CN103635259B CN201280031329.3A CN201280031329A CN103635259B CN 103635259 B CN103635259 B CN 103635259B CN 201280031329 A CN201280031329 A CN 201280031329A CN 103635259 B CN103635259 B CN 103635259B
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metal
nickel
reactor
coating
tin
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CN103635259A (zh
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沃尔夫冈·科尔曼
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    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
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    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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Abstract

本发明涉及用作光学流控反应器的催化材料，及其制备方法。在这方面可以首先制成网格化的塑料泡沫，然后将其用至少一种第一金属层或金属合金层涂层。随后，将光催化基底应用至金属层或金属合金层。在光学流控反应器使用时，光催化基底消除细菌、病毒和其它有害物质，以及细粒或真菌孢子。在备择方法中，在表面构成光催化活性的金属基质层。

Description

催化活性的、金属化的反应性泡沫材料的制备及其应用
本发明涉及光学流控反应器和随之用于消除细菌、病毒或细粒和真菌孢子和其它有害物质的催化材料。
在现有技术中已知的是，光催化基底用作光学流控反应器。一种这样的基底是例如二氧化钛(TiO2)-优选锐钛矿的四方、结晶形式。在阳光照射下后者释放电子，将污染物或其它有害物质破坏成为无害物质。氧化物的电子释放以及随之发生的光催化反应由一系列物理和化学过程组成。主要地，在氧化物表面通过游离电子形成氧自由基，其也称为活性氧。这些氧自由基包括游离的自由基，例如超氧化物阴离子、羟基自由基、过氧化氢自由基或烷氧基自由基，以及稳定的分子自由基，比如已知的过氧化物、过氧化氢、臭氧或次氯酸阴离子。在各种分子和有机尘粒与氧化物表面接触时，这些氧自由基将它们分解。活化的氧还有效分解气味物质和空气污染物，例如氮氧化物和有机细粒。更进一步地，这些氧杀死细菌和病毒-甚至是侵略性的病原体如SARS和H5N1也在与氧化物表面接触时得到很有效地抵抗。
本发明的任务尤其在于提供光学流控反应器，其展示高效率。
所述任务：
a)一方面通过制备催化材料解决，所述材料中组合光催化和流体-流通
b)另一方面通过提供涂层解决，其中在表面构成具有催化活性的金属或金属氧化物的金属基质。
在此，这两个方面能够有利地相互组合。
关于a)，出于流体流通的目的由例如聚醚砜(PES)或聚丙烯(PP)或聚乙烯(PE)或聚氨酯(PU)或聚酯或聚醚形成网格化的塑料泡沫，其作为基底泡沫被网格化。在网格化的情况下，使得单个泡沫室之间的薄间壁部分破裂，从而泡沫可透过流体。这样的泡沫具有极其巨大的表面，其在流体流通的情况下与后者接触。流体可以是清洁空气或清洁水。在这方面，光学流控反应器优选用于室内空气处理或水处理。
出于水处理目的，光学流控反应器能够植入透UV光层例如玻璃之间加以保护。然后，其用于待清洁水道的流通坡中。可以前置用于过滤粗悬浮物的预滤器。
有利地，这种适于流体-流通的网格化泡沫具有多至34ppi(孔/英寸)的孔数。比如说，孔数平均为9ppi(波动范围是8至10ppi)或平均为10.5ppi(波动范围8至13ppi)或平均为14.5ppi(波动范围是12至17ppi)或平均为19.5ppi(波动范围是16至23ppi)或平均为25.5ppi(波动范围是12至29ppi)或平均为30.5(波动范围是27至34ppi)。
然后，网格化的基底泡沫在进一步的方法步骤中用至少一种第一金属层或金属合金层涂层。由此泡沫经历固化，从而由此获得的固态复合材料可以例如以板形式用作腔室中的盖板或作为其中的分隔壁。通过这种金属涂层防止基底材料即泡沫的光导致的脆化。此外，这样涂层的泡沫通过金属或金属合金的适宜选择满足装饰性的要求。在此选择金属层厚，从而涂层的泡沫材料获得特定负载能力由此，在构成板的情况下，还能够防止复合材料的下陷或弯曲。通过选择金属层厚，可以良好地控制材料强度。还能够相继施加更多的金属层。适宜的层厚具有至少1(表数量)微米。一方面在薄泡沫板的情况下通过蒸镀(Bedampfens)进行的金属涂层保证良好结果；另一方面在较厚泡沫板的情况下湿法化学涂层方法具有优势，原因是其能够良好地涂层较厚泡沫，直至其中心。
作为涂层金属全部物理、热或湿法化学可沉积的金属或金属合金都是适当的。
金属涂层的泡沫-复合材料是有待随后施加的催化活性层，即光催化基底，的理想载体。作为适宜的光催化基底考虑二氧化钛(TiO2)-优选锐钛矿的四方、结晶形式-或由铜、镍、锌、锡、钴或锰组成的金属层，或金属合金或氧化物，以及单个氧化物的混合物。作为光催化基底适宜的是由银、钯或铂组成的贵金属层或由金属合金和组合物构成。
这样形成光学流控反应器，其由于其强度能够通过至少一个第一金属层用水或类似物容易地清洁，而不失去其效果。
上述根据本发明的由光催化和流体流通的组合展示光催化剂效率的极大改善。在泡沫中产生的于泡沫中分支的通道提供高表面/流体体积比，借此根据本发明的光学流控反应器实现更佳的清洁。
下面描述优选的实施方式：具有优选12-17ppi的孔数和10mm厚度的网格化塑料泡沫在第一涂层步骤中用数纳米至1(1μm)或更多微米厚的铜层涂层，其通过气相沉积、喷溅涂覆或电镀施加至泡沫上。随后，这种第一金属层通过额外的层通过电镀金属化用层厚大于20μm的铜、铁或铝强化。在这种铜层上，作为腐蚀保护电镀施加镍层、白青铜层或钴-锡层，其可以与抗过敏(antiallergenen)钴-锡-金属层组合。代替这些层或层组合，还可以施加例如钯、铂或银的贵金属层或由金属合金组成的贵金属层-以及与上述金属镍、锌、白青铜、钴或锡之一形成的金属合金的贵金属层。有利的是，层厚为至少5μm。
随后，通过泡沫的浸渍或流涂或喷射，将通过涂层获得的金属化材料用作为光催化基底的二氧化钛层涂层至其上。
涂层是在溶胶凝胶方法中制备的水基或溶剂基二氧化钛溶液。该涂层除了光催化效果以外还超亲水、自清洁和强抗微生物。
从成型体可以制成内部腔室盖板或腔室隔板，所述成型体由根据上文描述获得的材料构成，其由此清洁室内空气。能够在内部腔室搭建的设计元件是有利的，用以清洁室内空气。在这方面，可以构造不同的材料形式。在这些实施方式中，除了清洁室内空气的效果之外还值得提及的是隔音效果。由此，内部腔室元件可以直接用于大房间办公室以及噪音降低。
为了成型的目的，单独的光学流控元件例如板可以相互结合，例如粘合。在此应注意的是，充足的UV光能够透至如此结合的元件的中心并且保证流通。
经证明有利的是，其间植入UV灯的元件构成的反应器。从反应器中心向外发出UV光。除了发射UV光，经构入的灯还发射可见光，从而这样的反应器也充当光源。这样构入的灯还通过借此实现的灯对流通过产生的热导致光学流控反应器的强制流通
本发明还包括通风装置，其具有作为重要功能元件的如上文描述的光学流控反应器。这种通风装置经过通风设备或类似物使得空气强制流通光学流控反应器。光催化反应器的这种强制流通数倍地提高空气的清洁效果。以有利的方式，根据本发明的泡沫材料能够作为光学流控反应器在上述通风装置中容易地替换，也即卸下并清洁。
以有利的方式，根据本发明的光学流控反应器还可以用作空气抽吸罩的过滤体。它们在现有技术中用于厨房、或抽吸蒸气例如溶剂、焊烟或烟道气。
在用UV-A灯照射的情况下，光学流控反应器的光催化效果如上文已显示地以有利方式得以提高。在这方面通风装置、烟雾抽吸罩或内部腔室-成型体的有利实施方式具有这样的UV-A-灯，从而光学流控反应器能够按需要进行照射。在这方面还适当的是，从本发明金属化泡沫材料构造设计体，其用这样的UV-灯照射。
附图1和2是网格化基底泡沫的照片，其可以用作光学流控反应器的原材料。在此，附图2是附图1的泡沫的放大视图。
有关根据其在表面构成金属基质的解决方案变型b)，用于细菌、病毒和其它一般污染物的消毒的新涂层展示于下文。除了如上文所描述和解释用于各种不同应用的用于网格化基底泡沫的涂层，额外还提供不具流体动势(Durchflutung)的涂层应用，例如用于门把手、卫生设备，或者用于其接触的所有表面和由此中断细菌和病毒的污染。这涉及在私人居所、医院或公共设施中的应用。
已知的是，在电镀电解质中分散不同的物质例如金刚石粉末、SiC、Al2O3、CBN、WC、TiC、PTFE或石墨，并且用各自电解质电镀地(例如氨基磺酸镍、Watt′硫酸镍等)或无外电流地(例如化学镍)沉积在各自的构件上，以避免磨损、提高温度稳定性或改善摩擦特性。
根据本发明将TiO2-优选锐钛矿形式-为了用作光催化活性的分散体层，构成所谓的TiO2-金属基质层。
TiO2的优选粒径是0-3μm；例如KRONOClean7000和KRONOClean7050。
还可能的是使用大小约20nm的纳米级的TiO2颗粒；在此情况下，由于聚团问题悬浮体的制备可以是繁复昂贵的，但是可以实施的。在纳米级颗粒有助于利用分散化学品。
用例如TiO2-ENiP(TiO2，具有化学镍-磷金属层)或电镀NiP的用于涂层的基本方法过程描述于下文，用于空气清洁和水清洁的网格化泡沫，以及塑料构件：
1.在第一涂层步骤中，将网格化泡沫用优选＞1μm的铜层通过气相沉积或通过无外电流方法(化学铜)涂层。
2.这样的第一金属层通过电镀方式用铜、铁或铝(优选Cu)以大于10μm的层厚涂层，直至泡沫达到固有硬度(Eigensteifigkeit)。
3.向该层上施加额外的金属层或金属合金层例如Ni、白青铜(Weiβbronze)、黄铜(Gelbbronze)、NiP、Cr、NiCo、ENiCoP，层厚＞5μm。
4.向该层上施加光催化的例如NiP-TiO2层，层厚＞1μm。
还可以，将层厚＞1μm的Cu-TiO2层施加至第2点之后制备的第一金属层。
根据实施方式可能的是，将光催化层不具中间层地直接施加至铜层2上
根据实施方式还可能的是，向光催化层4上施加层例如硬铬或贵金属例如Au、Pd、Rt或Pt。
在金属工件的情况下，展开步骤1。
制备用于形成根据步骤4的具有TiO2-Ni沉积的金属基质的电解质的实施例：
Watt`scher(硫酸)镍电解质具有下述成分
采用这些成分可能实现多至50质量％的安装率(Einbaurate)。
根据实施方式还可能的是，为了防止成孔而使用湿润剂比如十二烷基硫酸钠或电镀化学品供应商的标准湿润剂。
TiO2颗粒通过电解质运动借助机械搅拌保持悬浮。温和通入空气是有利的。
各自精确的TiO2-浓度取决于希望的氧化物安装率和构件形状，以及构件的一般情况(表面粗糙度、微观形状等)。
搅拌速度和依赖构件形状和所用微观结构的所用电流密度也对安装率有重要影响。
准确保持pH值也是重要的，原因在于通过待沉积的TiO2-颗粒的制备仍可能附着残余物例如前体物质(碱性和酸性的)。TiO2-金属-基质沉积可以用各种不同的电解质作为基质金属。
作为电镀(用电流)制备的基质金属，所用的适宜的是NiP、Ni、Co、Cu、W、Mn、Mo、Cr、Sn、Zn、(硬铬)，贵金属比如Pd、Pt、钌、铑和由其组成的不同金属合金。还可使用氨基硫酸电解质或离子液体。
用无外电流方法比如化学镍-磷和各种不同的金属合金例如Ni-Co-P(肼还原剂)，Co-P，Ni-Cu-P，Ni-W-P，Ni-Mo-P和化学铜的基质金属也是适当的。
这种TiO2-沉积层的巨大优点是，催化活性颗粒牢固地固定在非常耐磨的金属基质中，和随之预计很长的有效持续时间。
额外地，随涂层逐渐磨损在每个时间点总有新TiO2-颗粒在表面释放，并且借此发挥作用直至涂层完全损耗。与在溶胶凝胶方法、涂漆方法(湿粉清漆)或薄层方法(溅射、气相沉积等)施加的涂层相反，本发明的涂层无可比拟地更长地保持金属基质，并且使得其非常适用于对磨损高要求的构件和需要频繁接触的表面，和比如尤其在医院中消毒各种细菌和病毒。
这样制备的TiO2-金属基质层具有巨大优点，其与光结合连续地分解门把手(Türkliniken)、握持表面等上的病毒和细菌，且由此除了清洁循环外还提供对抗接触传染疾病的感染和传播的尽可能大的安全性。
TiO2-颗粒向环境的进入也由于更少的磨损稳定的漆层得以最小化。
采用上述方法途径还可以涂层金属化的、织物基材料比如由塑料-、玻璃-或碳材料制成的羊毛(Vliese)、织物等。

Claims (8)

1.用于消除有害物质的催化材料的制备方法，包括
a)将网格化的塑料泡沫制成厚度至少10mm的板；
b)将数种金属层施加至网格板的表面，其中金属是铜；
c)在溶胶凝胶方法中，通过浸渍、流涂或喷射从溶液施加光催化TiO2基底；
其特征在于，在步骤b)之后步骤c)之前，施加铝、镍、锡、锌、银、钯、铂或其金属合金的额外金属层。
2.根据权利要求1的方法，其特征在于所述额外金属层的金属选自镍、锡、银或其合金。
3.用于消除有害物质的催化材料，包含
a)用层厚至少10mm的网格化塑料泡沫制得的板；
b)板上的数个金属层，所述金属是铜；
c)在溶胶凝胶方法中，通过浸渍、流涂或喷射从溶液施加的光催化TiO2基底；
其特征在于，在b)数个铜层与c)光催化TiO2基底之间施加额外的金属层，所述额外的金属层由铝、镍、锡、锌、银、钯、铂或其金属合金制成。
4.根据权利要求3的催化材料，其特征在于所述额外的金属层的金属选自镍、锡、银或其金属合金。
5.用于从流体消除细菌、病毒、真菌孢子、细粒和其它有害物质的反应器，包含根据权利要求3或4的催化材料的板并且具有植入其间的UV灯。
6.根据权利要求5的反应器，其特征在于所述流体是待清洁的空气。
7.根据权利要求6的反应器，其特征在于所述反应器还包括通风装置。
8.根据权利要求5的反应器，其特征在于所述流体是待清洁的水。
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