CN107649110B - 形成具有铂原子的原子层的催化剂的方法 - Google Patents
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 23
- 150000003057 platinum Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004094 surface-active agent Substances 0.000 description 13
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Abstract
形成催化剂材料的方法，其包括阻碍置换反应的反应速率和控制铂簇的形成，其中用铂原子置换金属原子的原子层，以产生包含铂原子的原子层的催化剂材料。
Description
本申请是申请号为201180068250.3(PCT/US2011/025693)、申请日为2011年2月22日、发明名称为“形成具有铂原子的原子层的催化剂的方法”的中国专利申请的分案申请。
技术领域
本发明涉及产生具有更均匀的铂原子的原子层的催化剂材料的方法。
背景技术
在电化学反应（例如在燃料电池内产生电流的电化学反应）中，铂是已知的，并用作催化剂材料。可将铂沉积在承载在碳颗粒上的贵金属的金属核上。为了增大铂的物质活性（mass activity），以贵金属核上的薄层形式来提供铂。
用于制备此类催化材料的一种常规制造方法涉及首先将具有比铂低的还原电势的金属原子薄层沉积到贵金属核颗粒上。一些制造者使用欠电势（underpotential）沉积方法来沉积作为较低还原电势金属的铜原子。然后将核颗粒与含有铂盐的溶液混合。溶液中的铂原子自发地置换贵金属核上的铜原子，以产生在贵金属核上的铂原子薄层。
发明内容
公开的是形成催化剂材料的方法，其包括阻碍置换反应的反应速率，其中用铂原子置换金属原子的原子层，以产生包含铂原子的原子层的催化剂材料。
另一方面，形成催化剂材料的方法包括在表面活性剂的存在下，用铂原子置换金属原子的原子层，以产生包含铂原子的原子层的催化剂材料。
还公开的是形成催化剂材料的方法，其包括以下步骤：提供包含被金属原子的原子层覆盖的金属核的颗粒，提供包含表面活性剂和铂盐的溶液，和用所述溶液处理所述颗粒，以用来自该溶液的铂原子置换所述金属原子，并产生包含被铂原子的原子层覆盖的金属核的催化剂材料。
附图说明
从下列详述，对于本领域技术人员来说，所公开的实例的各种特征和优点将变得明显。可将该详述所随附的图简单描述如下。
图1图解了示例性催化剂材料。
图2图解了通过欠电势沉积来沉积金属的原子层的实例。
图3图解了使用表面活性剂来阻碍反应速率的置换反应的实例。
具体实施方式
图1示意性地图解了示例性催化剂材料20的所选部分，所述催化剂材料20具有高度活性，并可用于燃料电池或其它催化环境中。在该实例中，催化剂材料20包含碳载体（carbonsupport）22和附着于该碳载体的表面上的金属核24。金属核24被壳26覆盖。壳26是铂原子的原子层。金属核24可以是贵金属或金属（例如铂、金或其它贵金属）的混合物。
在实施方式中，壳26是原子单层(即，一个原子厚度)。然而，虽然壳26通常具有均匀厚度，但是应理解，壳26的一些部分可以是较薄的（亚单层（submonolayer））或较厚的（数个原子厚度）。
如将进一步详述的，用于在金属核24上形成壳26的方法产生了铂原子的原子层的更均匀厚度，从而增强了铂的物质活性。
用于形成壳26的方法涉及置换反应，其中铂原子置换金属核24上较低还原电势的金属原子。在一些实例中，较低还原电势的金属原子是铜。使用欠电势沉积方法(UPD)可将铜沉积在金属核24上。UPD是用于沉积原子层厚度的铜原子的临时性壳28的技术。然后用包含铂的溶液来处理金属核24和铜的临时性壳28。
在常规方法中，溶液中的铂原子自发地置换较低还原电势的铜原子，以产生铂原子的原子层。自发置换的反应速率快，导致铂原子壳的厚度的变化。换言之，铂原子并不基于一对一的方式（on a one-for-one basis）来置换铜原子。反而铂原子倾向于成簇（cluster）或留下金属核的一些部分（portions）未被覆盖。
本文公开的方法涉及阻碍置换反应的反应速率和控制或减少铂原子在现有的铂上的沉积，以提供铂原子壳26对金属核24更均匀的覆盖。在一个实例中，在表面活性剂的存在下进行本公开方法的置换反应，所述表面活性剂例如是柠檬酸和/或乙二胺四乙酸(EDTA)，其阻碍或减慢反应速率以实现用铂原子受控制地置换铜原子。表面活性剂与铂盐形成配位化合物。换言之，铂盐更难以还原，从而减慢置换反应的反应速率。在减慢的反应速率下，铂原子较不倾向于成簇或在金属核24的表面上留下敞开的部分（open portions）。从而所得的壳26具有更均匀的厚度和相应的较高的物质活性。表面活性剂也可阻碍铂原子在现有的铂原子上的沉积。表面活性剂通过吸附在现有的铂原子上来与新还原的铂原子竞争，以致铂原子只能沉积在金属核24上。从而减少铂簇的形成。
图2示意性地描述了示例性的UPD方法。最初，在图的左侧，反应之前在碳载体（未示出）上提供一个或更多个金属核24。然后在UPD方法中处理金属核24，以将临时性的铜原子壳28沉积在金属核24上。所得的铜原子薄层可具有从亚原子厚度到数个原子厚度变化的原子厚度。在实施方式中，临时性壳28基本上是原子单层。
如图3中所图解的，然后在置换反应中将临时性壳28的铜原子置换，以在金属核24上产生铂原子壳26。在这个实例中，在表面活性剂的存在下进行置换反应，以减慢反应速率和控制或减少铂原子在现有的铂原子上的沉积，从而如上所述产生均匀的铂原子的原子层。
在实施方式中，在溶液中提供表面活性剂，金属核24混合在所述溶液中。例如，所述溶液可包含稀酸、表面活性剂、和铂盐以提供铂原子。所述稀酸可以是硫酸。所述表面活性剂可选自柠檬酸、乙二胺四乙酸(EDTA)、一氧化碳或其混合物。所述表面活性剂通过形成配位化合物来阻碍置换反应，或通过吸附在现有的铂原子上来减少铂簇的形成。以下是所公开的方法的另外实例。
实施例 1
铂单层催化剂的制备
将Pd/C粉末直接松散地置于石墨片或铸件（cast）上，并压在基材上。
任选地，通过以下方式来清洁Pd/C：(a) 将Pd/C粉末的溶液与稀硫酸混合，并建立该溶液的电势，其在氢气释放（evolution）区(例如，相对RHE -50mV)，(b)对Pd/C粉末进行电势循环（potential cycling）(例如，用10mV/s的扫描速率以0.5-1.1V进行许多循环)或(c)用氢气吹扫Pd/C粉末30分钟。
将Pd/C粉末的电势保持在铜UPD电势，所述铜UPD电势是在Cu2+(0.2 M CuSO4)和稀酸(0.5 M H2SO4)的溶液中经一定时间（例如2小时）预先确定的。或者，将该溶液电势循环，以确定铜UPD电势。任选地，循环之后，将溶液保持在那个电势下大约30分钟。
制备铂盐(例如K2PtCl4)在稀酸(例如0.05 M H2SO4)中的溶液。铂盐的量大约是用来替换Pd/C粉末上的所有铜原子的计算量的1.1至3倍。然后以3.5 mM或更高的浓度将柠檬酸加入到溶液中。
然后将铂盐溶液与含有Pd/C粉末的溶液混合，以产生催化剂。所述混合可包括使用滴管或移液管将含有Pd/C粉末的溶液加入到铂盐溶液中。可超声振荡该溶液，以分散Pd/C粉末。
然后将催化剂从溶液中过滤出来并用热水洗。可通过用氢气吹扫或用稀酸清洗来进一步清洁该催化剂。
实施例1中生产的催化剂显示相对高的物质活性。由实施例1生产的催化剂显示0.6 A/mg的铂物质活性。相比之下，没有表面活性剂的条件下生产的催化剂显示0.36 A/mg的铂物质活性。
虽然在在图解的实例中显示了各特征的组合，但并不需要所有特征组合来实现本公开内容的各种实施方式的益处。换言之，根据本公开内容的实施方式设计的系统不必需包含任一附图中显示的所有特征或在附图中示意性地显示的所有部分。另外，一个示例性实施方式的选择特征可与其它示例性实施方式的选择特征组合。
前文的描述在性质上是示例性的而非限制性的。对公开的实例的变更和改变对于本领域技术人员可变得显然，而不必需背离本公开内容的本质。给予本公开内容的法律保护范围只能通过研究随附权利要求书来确定。
Claims (10)
1.形成催化剂材料的方法，所述方法包括：
阻碍置换反应的反应速率以控制铂簇的形成，其中用铂原子置换金属原子的原子层，以产生包含铂原子的原子层的催化剂材料，其中所述阻碍包括：
A)在铂配位性化合物的存在下进行置换反应；和
B)在置换反应期间用铂配位性化合物和i)铂盐；或ii)铂原子的原子层形成配位化合物，从而阻碍用铂原子置换金属原子，
其中所述金属原子包括铜，和
其中所述金属原子的原子层在贵金属核上。
2.根据权利要求1所述的方法，其中所述铂配位性化合物是柠檬酸。
3.根据权利要求1所述的方法，其中所述铂配位性化合物是乙二胺四乙酸(EDTA)。
4.形成催化剂材料的方法，所述方法包括：
在铂配位性化合物的存在下用铂原子置换金属原子的原子层，以产生包含铂原子的原子层的催化剂材料，所述方法进一步包括在金属原子的原子层的置换期间，用所述铂配位性化合物和i)铂盐；或ii)铂原子的原子层形成配位化合物，
其中所述金属原子包括铜，和
其中所述金属原子的原子层在贵金属核上。
5.根据权利要求4所述的方法，其中所述铂配位性化合物选自柠檬酸、EDTA及其混合物。
6.根据权利要求4所述的方法，其中所述铂配位性化合物与酸和所述铂盐在溶液中。
7.形成催化剂材料的方法，所述方法包括：
提供包含金属核的颗粒，所述金属核被金属原子的原子层覆盖；
提供包含铂配位性化合物和铂盐的溶液；和
用所述溶液处理所述颗粒，从而用铂原子置换所述金属原子，并产生包含被所述铂原子的原子层覆盖的金属核的催化剂材料；和
通过在金属原子的置换期间用所述铂配位性化合物和i)铂盐；或ii)铂原子的原子层形成配位化合物来阻碍用铂原子置换金属原子，
其中所述金属原子包括铜，和
其中所述金属核是贵金属核。
8.根据权利要求7所述的方法，其进一步包括使用欠电势沉积(UPD)将所述金属原子的原子层沉积到所述金属核上。
9.根据权利要求7所述的方法，其中所述铂配位性化合物选自柠檬酸、EDTA及其混合物。
10.根据权利要求7所述的方法，其中用所述溶液处理所述颗粒包括将所述颗粒与所述溶液混合。
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