CN107249739A - 用于形成催化纳米涂层的方法 - Google Patents
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 35
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- 239000011248 coating agent Substances 0.000 title claims abstract description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 46
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
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- 150000002739 metals Chemical class 0.000 claims abstract description 17
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- 230000015572 biosynthetic process Effects 0.000 claims description 9
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
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- 238000003786 synthesis reaction Methods 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
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- 238000000508 aqueous-phase reforming Methods 0.000 claims description 4
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- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
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- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
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- 238000001354 calcination Methods 0.000 claims 1
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- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- 238000007669 thermal treatment Methods 0.000 claims 1
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- 238000000231 atomic layer deposition Methods 0.000 description 16
- 238000000151 deposition Methods 0.000 description 8
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Abstract
本发明涉及一种在金属板的表面上形成催化纳米涂层的方法，其中该方法包括借助于500℃‑800℃下的热处理来预处理该金属板的表面，通过在该金属板的表面上洗涂来形成金属氧化物载体，并且借助于原子层沉积(ALD)方法将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上来涂覆该金属板的表面，以便在该金属板上形成薄且共形的催化剂层。此外，本发明涉及一种催化剂和用途。
Description
技术领域
本发明涉及一种在权利要求1的前序部分中限定的用于形成催化纳米涂层方法。此外，本发明涉及一种在权利要求11的前序部分中定义的催化剂以及一种在权利要求13的前序部分中定义的用途。
背景技术
用于制备催化剂的不同方法是从现有技术中已知的。在本领域中，存在在结构和材料两者上不同的若干类型的催化剂。一种特定类型的催化剂由其上已经沉积了催化活性层的金属基底组成。
用于沉积活性层的若干种方法是从现有技术中已知的。典型地，通过使用氧化铝或另一种金属氧化物浆料洗涂来将该催化活性层加入该金属基底中，该浆料含有呈盐、氧化物或元素金属的形式的催化活性金属。基底还可以首先用金属氧化物浆料洗涂，并且然后可以使用传统方法如浸渍进行催化剂金属加入。在这些方法中，难以控制金属颗粒的尺寸、分散体或层的厚度。因此，为了获得高的催化活性，必须使用过度高的金属负载量。由于催化活性金属在许多情况下变得越来越昂贵，并且它们中的许多是稀有且战略性的金属，有益的是例如减少催化反应器中的金属负载量。
此外，从现有技术中已知用于涂覆不同材料的原子层沉积(ALD)方法。
发明目的
本发明的目的是披露一种用于形成催化纳米涂层的新型方法。此外，本发明的目的是披露了一种用于形成新型催化剂的方法。
发明内容
根据本发明的方法的特征是在权利要求中已经呈现的那些。
本发明基于一种用于在金属板的表面上形成催化纳米涂层的方法。该方法包括：借助于500℃-800℃下的热处理来预处理该金属板的表面，通过在该金属板的表面上洗涂来形成金属氧化物载体(例如Al2O3载体)，并且借助于原子层沉积(ALD)方法将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上来涂覆该金属板的表面，以便在该金属板上形成薄且共形的催化剂层。
在本发明中，预处理金属板的表面，并且通过使用ALD技术在该金属板上形成催化活性金属和/或金属氧化物的催化纳米涂层。在本发明中，该催化纳米涂层可以直接被安排到该金属板上。当在高温下预处理该金属板时，可以改变该金属板的表面的结构。然后可以在该金属板上形成具有永久和耐用特性的催化纳米涂层。
此外，本发明基于在该金属板的表面上包含催化纳米涂层、优选催化剂层的催化剂，并且，根据在此上下文中呈现的方法，该催化纳米涂层已经形成到该金属板的表面上。该催化纳米涂层是催化活性涂层。
作为催化纳米涂层(优选地催化剂层)适合的并且本身已知的通过原子层沉积(ALD)方法形成的任何材料可以用于本发明的方法中。该原子层沉积(ALD)是薄膜沉积工艺，其应用薄膜制备的自限制和顺序表面反应。ALD使用挥发性或气态化学品(如前体)来生长共形薄膜。在第一ALD步骤期间，将含有元素A的分子引入到基底的表面上，并且这些第一分子被吸附在该表面上。然后将含有元素B的第二分子引入用于在该表面处与元素A反应，并且然后实现一个化合物AB层。重复这种程序，直到实现所希望的膜厚度。同样可以应用与ALD技术相关的其他反应机制。
在此上下文中，金属氧化物载体可以包含任何金属氧化物或不同金属氧化物的任何混合物。此外，该金属氧化物载体可以包含其他组分，例如合适的粘合剂和/或填料试剂。在一个实施例中，该金属氧化物载体由一种或多种选自下组的金属氧化物形成，该组由以下各项组成：Al2O3、MgO、TiO2、其他合适的金属氧化物及它们的组合。在一个实施例中，该金属氧化物载体是包含Al2O3的Al2O3载体。
在此上下文中，催化活性金属和/或金属氧化物可以包括任何合适的金属，该金属是催化活性金属。在一个实施例中，金属选自下组，该组由以下各项组成：Co、Ni、Mo、Zr、Ti、Hf、贵金属、其他合适的金属及它们的组合。
在此上下文中，金属板可以是任何金属板、金属膜、金属盘、金属面板、金属片、金属泡沫、金属过滤器管或类似物。该金属板可以是光滑板或波纹状或另外非平面结构，如热交换器板。
在一个实施例中，通过优选地在500℃-800℃之间的温度下氧化来热处理该金属板的表面。
在一个实施例中，该金属板的表面用基于金属氧化物的浆料例如基于Al2O3的浆料来洗涂。
在一个实施例中，通过喷雾进行该洗涂。在一个实施例中，通过浸涂进行该洗涂。可替代地，该洗涂可以通过其他合适的方法进行。
在一个实施例中，在500℃-800℃下煅烧该通过洗涂形成的金属氧化物载体，优选地在该洗涂之后在500℃-800℃下煅烧该金属氧化物载体。
在一个实施例中，在将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上期间调节沉积温度。
在一个实施例中，借助于原子层沉积(ALD)方法在50℃-700℃下将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上。在一个实施例中，在约100℃-300℃下将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上。在一个实施例中，在140℃-160℃下、优选地在约150℃下将催化活性Co氧化物沉积在该金属氧化物载体上。
在一个实施例中，可以通过改变沉积温度或增加沉积时间来调节该金属板上的表面覆盖度。
在一个实施例中，该催化剂层的厚度是在1-500nm之间。
在一个实施例中，三(2,2,6,6-四甲基-3,5-庚二酮酸)钴和臭氧用作该原子层沉积(ALD)中的前体。可替代地，任何其他合适的前体可以用于该原子层沉积(ALD)中。
催化剂可以形成有不同结构，在一个实施例中，形成有整体件。在一个实施例中，该催化剂用于催化反应器、自清洁表面、生物质衍生的化学品的生产、运输燃料的生产、FT合成、用于燃料电池应用的重整器、用于合成气应用的气体处理单元或用于生物精炼厂的水相重整器中。
在一个实施例中，该方法用于在反应器如催化反应器、燃料电池应用的重整器和用于生物精炼厂的水相重整器，以及工艺如生物质衍生的化学品的生产、运输燃料的生产、FT合成和用于合成气应用的气体处理单元和自清洁表面的生产以及它们的组合中形成催化纳米涂层。
包括预处理该金属表面以及通过使用ALD方法用催化活性金属和/或金属氧化物涂覆该金属表面的组合对于本发明是重要的。由于本发明，可以在该金属板上产生耐用且具有高表面积和低催化剂负载量的催化纳米涂层。由于本发明，该催化纳米涂层可以直接形成在该金属板上。本发明的表面受控制的方法使能够严格控制金属或金属氧化物沉积。这种纳米涂层可以容易地应用于不同的纳米涂层。
本发明提供了可以实现具有良好品质的催化剂并且可以减少催化剂中的金属负载量的优点。由于本发明，活性催化剂可以用最少量的金属来制备。这在基于使用催化剂的许多工业工艺中使能够降低投资和操作成本。由于本发明，可以改进反应器生产量。
此外，本发明的组合开辟了改进在各种生物质衍生的化学品和运输燃料的生产工艺中的技术和经济可行性的可能性。
本发明提供了一种工业上可应用的、简单并且负担得起的生产催化纳米涂层的方式。本发明的方法作为生产工艺是容易且简单实现的。
附图列表
在以下的部分中，本发明将借助于详细的示例性实施例、参照附图进行描述，其中
图1呈现了根据本发明的一个实施例的方法的流程图说明。
具体实施方式
图1呈现了根据本发明用于形成催化纳米涂层的方法。
实例1
在图1的方法中，在金属板的表面上形成催化纳米涂层。
借助于500℃-800℃下氧化的热处理来预处理(1)金属板的表面。通过在已预处理的金属表面上洗涂(2)形成该金属氧化物载体如Al2O3载体，使得将该金属表面用基于金属氧化物的浆料如基于Al2O3的浆料通过喷雾或浸涂来洗涂。在500℃-800℃下煅烧(3)该金属表面上的洗涂的载体。借助于原子层沉积(ALD)方法将这些催化活性金属和/或金属氧化物如Co氧化物沉积(4)在已经涂覆有该金属氧化物载体的金属表面上。在140℃至300℃之间的温度下将这些催化活性金属和/或金属氧化物沉积在该金属氧化物载体上。三(2,2,6,6-四甲基-3,5-庚二酮酸)钴和臭氧用作该ALD方法中的前体。氮气用作载体和吹扫气体。取决于循环数目，在该金属氧化物载体上形成具有在1-500nm之间的厚度的催化剂层。
这些金属和/或金属氧化物可均匀地分散在该金属氧化物载体上，并且在高温下它们还很好地粘附在该表面上。
实例1和本发明中使用的装置本身是已知的，并且因此在此上下文中不更详细地描述它们。
实例2
在这个测试中，研究了工艺条件。
Picosun Sunale R-200ALD反应器用于以单晶片模式沉积CoOx。Co(thd)3即三(2,2,6,6-四甲基-3,5-庚二酮酸)钴(abcr GmbH&Co.KG，纯度99％)和臭氧(O3)(O2 99.999％纯度，AC-SERIES臭氧发生器，IN美国公司)用作前体。氮气(99.999％)用作载体和吹扫气体。
测试不同的沉积温度、前体温度、脉冲和吹扫时间和线流，以便找到膜生长的最佳参数。在优化沉积参数之后，在约150℃下进行CoOx沉积。通过椭圆计(SE400adv，森泰科仪器公司(SENTECH Instruments))测量Si参考基底上的膜厚度。在150℃下沉积速率是大约/循环。在ALD沉积之后，通过现有方法评估催化活性。观察到的是实现催化活性。
根据本发明的方法在用于形成不同催化纳米涂层的不同实施例中是合适的。根据本发明的方法在用于形成不同种类的催化剂的不同实施例中是合适的。
本发明不仅仅限于上面所涉及的实例；而是，许多变化有可能在权利要求书限定的本发明思想的范围内。
Claims (13)
1.一种用于在金属板的表面上形成催化纳米涂层的方法，其特征在于，该方法包括
-借助于500℃-800℃下的热处理来预处理该金属板的表面，
-通过在该金属板的表面上洗涂来形成金属氧化物载体，并且
-借助于原子层沉积(ALD)方法将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上来涂覆该金属板的表面，以便在该金属板上形成薄且共形的催化剂层。
2.根据权利要求1所述的方法，其特征在于，通过氧化热处理该金属板的表面。
3.根据权利要求1或2所述的方法，其特征在于，用基于金属氧化物的浆料洗涂该金属板的表面。
4.根据权利要求1至3中任一项所述的方法，其特征在于，该洗涂通过喷雾或浸涂进行。
5.根据权利要求1至4中任一项所述的方法，其特征在于，在该洗涂之后在500℃-800℃下煅烧该金属氧化物载体。
6.根据权利要求1至5中任一项所述的方法，其特征在于，借助于原子层沉积(ALD)方法在50℃-700℃下将催化活性金属和/或金属氧化物沉积在该金属氧化物载体上。
7.根据权利要求1至6中任一项所述的方法，其特征在于，该催化剂层的厚度是在1-500nm之间。
8.根据权利要求1至7中任一项所述的方法，其特征在于，三(2,2,6,6-四甲基-3,5-庚二酮酸)钴和臭氧用作该原子层沉积(ALD)中的前体。
9.根据权利要求1至8中任一项所述的方法，其特征在于，该金属氧化物载体包括Al2O3、MgO、TiO2、其他金属氧化物或它们的组合。
10.根据权利要求1至9中任一项所述的方法，其特征在于，催化活性金属和/或金属氧化物包括选自组Co、Ni、Mo、Zr、Ti、Hf、贵金属、其他合适的金属及它们的组合中的金属。
11.一种催化剂，其特征在于，该催化剂包含在该金属板的表面上的催化纳米涂层，并且该催化纳米涂层通过如权利要求1至10中任一项所述的方法已经形成到该金属板的表面上。
12.根据权利要求11所述的催化剂，其特征在于，该催化剂用于催化反应器、自清洁表面、生物质衍生的化学品的生产、运输燃料的生产、FT合成、用于燃料电池应用的重整器、用于合成气应用的气体处理单元或用于生物精炼厂的水相重整器中。
13.如权利要求1至10中任一项所述的方法的用途，其中该方法用于在反应器如催化反应器、燃料电池应用的重整器和用于生物精炼厂的水相重整器，以及工艺如生物质衍生的化学品的生产、运输燃料的生产、FT合成和用于合成气应用的气体处理单元和自清洁表面的生产以及它们的组合中形成催化纳米涂层。
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| CN114042452A (zh) * | 2021-12-03 | 2022-02-15 | 中汽研（天津）汽车工程研究院有限公司 | 一种用于柴油车尾气的氨氧化催化剂、制备方法及其应用 |
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| CN101521281A (zh) * | 2008-02-27 | 2009-09-02 | 通用汽车环球科技运作公司 | 低成本燃料电池双极板及其制造方法 |
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| EP2475802B1 (en) * | 2009-09-10 | 2014-08-13 | Northwestern University | Metal containing composites |
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| US20060216884A1 (en) * | 2005-03-23 | 2006-09-28 | Choi Hyung B | Methd for forming capacitor of semiconductor device |
| CN101439283A (zh) * | 2007-09-27 | 2009-05-27 | 通用汽车环球科技运作公司 | 纳米管组件、双极板及其制造方法 |
| CN101521281A (zh) * | 2008-02-27 | 2009-09-02 | 通用汽车环球科技运作公司 | 低成本燃料电池双极板及其制造方法 |
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| CN108671918A (zh) * | 2018-04-12 | 2018-10-19 | 华中科技大学 | 基于原子层沉积定向调控提高催化剂活性及选择性的方法 |
| CN114042452A (zh) * | 2021-12-03 | 2022-02-15 | 中汽研（天津）汽车工程研究院有限公司 | 一种用于柴油车尾气的氨氧化催化剂、制备方法及其应用 |
| CN114042452B (zh) * | 2021-12-03 | 2024-03-15 | 中汽研汽车检验中心（天津）有限公司 | 一种用于柴油车尾气的氨氧化催化剂、制备方法及其应用 |
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