CN101405080A - 稳定的浓金属胶体及其制备方法 - Google Patents
稳定的浓金属胶体及其制备方法 Download PDFInfo
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- CN101405080A CN101405080A CNA2007800092694A CN200780009269A CN101405080A CN 101405080 A CN101405080 A CN 101405080A CN A2007800092694 A CNA2007800092694 A CN A2007800092694A CN 200780009269 A CN200780009269 A CN 200780009269A CN 101405080 A CN101405080 A CN 101405080A
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Abstract
本发明提供了制备含金属的胶体的方法，包括使大量金属离子和大量有机试剂分子反应，在pH大于约4.25的混合物中形成金属络合物。将该金属络合物还原至少0.5分钟，形成稳定的胶态纳米颗粒。与短时间还原相比，长时间还原提高了胶态颗粒的稳定性。胶态颗粒的稳定性使得胶体可以具有较高的金属浓度。胶体中金属的浓度优选至少约为150重量ppm。
Description
发明背景
I.发明领域
本发明涉及用于制备催化剂的胶态纳米颗粒的制备。更具体地，本发明涉及制备稳定的浓胶体的方法。
II.相关技术
微粒催化剂是精炼、有机合成、精细化学制造之类的工业应用和许多其它工业方法的重要组分。许多这些催化反应需要使用贵金属，例如铂和钯。在制造对于给定量的贵金属可以提高产率的高性能催化剂方面已经进行了许多努力。
一种制备高性能催化剂的技术是使用金属盐和有机分散剂在溶液中形成颗粒。将金属盐溶解在溶剂中，与有机试剂反应，然后还原形成分散在溶剂中的纳米颗粒。因为颗粒非常小，例如小于1微米，所以分散的颗粒形成胶体。所述胶态的颗粒通常沉积在催化剂载体上。
通过胶体法制备催化剂的一个问题是必须保持较低的金属浓度以防止金属沉淀和团聚。使用已知的制备方法尝试制备浓胶体，结果造成贵金属颗粒的损失。浓缩胶体会使颗粒不稳定，导致颗粒团聚和/或沉淀。沉淀的颗粒不适合用作高性能催化剂，并且/或者不容易沉积在载体材料上。
因此，现有的制备负载型纳米颗粒催化剂的方法是使用具有稀浓度金属颗粒的金属胶体。低浓度金属胶体有时难以使用，因为需要较多的溶剂。如果胶体要进行运输，那么过多的溶剂重量和体积会明显增加运输成本。另外，将颗粒施加到载体材料上是更困难和昂贵的，因为必须除去过量的溶剂。
发明概述
本发明提供一种制备含有金属纳米颗粒的稳定的浓胶体的方法。该稳定的浓胶体是由金属离子和有机试剂制成的。在金属离子和有机试剂之间形成的络合物随后通过还原剂还原。还原剂作用于反应混合物的时间至少为30分钟，以还原金属原子，提高混合物中形成的纳米颗粒的稳定性。较佳地，反应混合物的pH最初至少约为4.25。
本发明的制备纳米颗粒的方法通常包括(i)提供大量催化金属原子，(ii)提供大量有机试剂分子，各有机试剂分子包含至少一个能与金属原子结合的官能团，(iii)使所述金属原子与有机试剂分子在溶剂中反应，形成包含大量络合的金属原子的混合物，该混合物的pH至少约为4.25，(iv)使用还原剂使混合物中络合的金属原子还原30分钟以上，这样在混合物中形成稳定的胶态纳米颗粒。
有机分散剂包含至少一个能与催化剂原子结合的官能团。有机分散剂还包含一个或多个用于与载体材料结合的官能团。用于与催化剂原子和/或载体材料结合的合适的官能团的例子包括一个或多个选自以下的基团：羟基、羧基、羰基、胺、酰胺、腈、具有游离孤对电子的氮、氨基酸、硫醇、磺酸、磺酰卤和酰卤。在一个优选的实施方式中，有机分散剂是聚丙烯酸或聚丙烯酸盐。
通过长时间还原络合的金属离子而带来的胶体的稳定化作用是令人惊奇和出乎意料的，因为预期还原将在20分钟内完成。据信对金属原子还原30分钟以上可以通过消除会导致团聚的部分还原的金属原子(即阳离子性金属原子)而使反应中形成的金属颗粒稳定。在pH值高于约4.25、更优选高于4.75、最优选高于5.0时，用还原剂处理了30分钟或更长时间的络合的金属原子往往不会团聚，从而减少了金属原子和/或纳米催化剂颗粒的沉淀。
胶体的稳定性对制备浓度更高的胶体的能力有着积极的影响。因为颗粒的形成产生质子，所以更浓的金属原子的混合物将得到pH更低的胶体。在金属的稀溶液中，溶剂将更容易缓冲质子浓度的增加。但是，通过本发明的长时间还原来稳定金属原子，可以在较低pH值下得到稳定胶体。
通过以下说明和所附权利要求可以更全面地明白本发明的这些和其它优点和特征。
优选实施方式的详细说明
I.引言
本发明涉及含有金属纳米颗粒的金属胶体，该胶体的制备方法，以及由该胶体制备的负载型纳米催化剂。制备含金属的胶体的方法通常包括使大量金属离子和大量有机试剂分子在溶液中反应，在pH大于约4.25的混合物中形成金属络合物。将该金属络合物还原至少30分钟，形成稳定的胶态纳米颗粒。与短时间还原相比，长时间还原提高了胶态颗粒的稳定性。胶态颗粒的稳定性使得胶体可以具有较高的金属浓度。
为了本发明的目的，术语“粒度”指平均粒度，“纳米颗粒”指粒度在约1纳米至1000纳米之间的颗粒。
II.用于制备含金属的胶体和负载型催化剂的组分
A.催化金属离子
任何可以与有机试剂分子反应形成络合物的金属或金属组合可用于形成本发明的胶体。催化金属可以表现出主要的催化活性，或者用作促进剂或改性剂。示例性金属包括贵金属、过渡贱金属(base transition metal)和稀土金属。
可表现出催化活性的过渡贱金属的例子包括但不限于钛、钒、铬、锰、铁、钴、镍、铜、锌、锆、钼、锡、锑、钨等。这些金属可以单独使用，或者以各种组合形式使用，或者与其它元素如贵金属、碱金属、碱土金属、稀土金属或非金属组合使用。
表现出催化活性的贵金属(也称为铂族金属)，的例子包括铂、钯、铱、金、锇、钌、铑、铼等。这些金属可以单独使用，或者以各种组合形式使用，或者与其它元素如过渡贱金属、碱金属、碱土金属、稀土金属或非金属组合使用。
表现出催化活性的稀土金属的例子包括但不限于镧和铈。这些金属可以单独使用，或者以各种组合形式使用，或者与其它元素如过渡贱金属、贵金属、碱金属、碱土金属或非金属组合使用。
任选地，还可以包括非过渡金属，它们通常作为促进剂或改性剂。合适的非过渡金属包括碱金属和碱土金属，例如钠、钾、镁、钙等和非金属，例如磷、硫、氧和卤素。
B.有机分散剂和有机分散剂分子
有机分散剂也称为分散剂或有机试剂，对其进行选择，以促进具有所需的尺寸、稳定性和/或均一性的纳米催化剂颗粒的形成。分散剂分子与金属离子反应，形成与金属离子络合的配体。
适用于结合金属离子的分散剂包括各种小有机分子、聚合物和低聚物。分散剂与溶解或分散在合适的溶剂或载体中的金属离子相互作用并结合。结合可以通过各种合适的机理形成，包括离子结合、共价结合、范德华力相互作用/结合、孤对电子结合或氢键结合。
为了提供分散剂分子和金属原子之间的结合，分散剂分子包括一个或多个合适的官能团。在一个实施方式中，所述官能团包括与至少一个富电原子结合的碳原子，该富电原子的电负性大于碳原子的电负性，能够给予一个或多个电子，从而所述碳原子与金属离子形成键或引力。优选的分散剂包含具有电荷或一个或多个能用于与金属离子络合的孤对电子的官能团。这些官能团使分散剂与金属离子之间形成强的结合相互作用。
在一个示例性实施方式中，分散剂的官能团包含一个或多个选自以下的基团：羟基、羧基、羰基、胺、酰胺、腈、具有游离孤对电子的氮、氨基酸、硫醇、磺酸、磺酰卤和酰卤。所述分散剂可以是单官能、双官能或多官能的。
合适的单官能分散剂的例子包括乙醇和丙醇之类的醇以及甲酸和乙酸之类的羧酸。可用的双官能分散剂包括：二元酸，例如草酸、苹果酸、丙二酸、马来酸、丁二酸等；二醇，例如乙二醇、丙二醇、1，3-丙二醇等；羟基酸，例如乙醇酸、乳酸等。可用的多官能分散剂包括糖如葡萄糖，多官能羧酸如柠檬酸、EDTA、果胶、纤维素等。其它可用的分散剂包括乙醇胺，巯基乙醇，2-巯基乙酸酯，氨基酸如甘氨酸，磺酸如磺基苯甲醇，磺基苯甲酸，磺基苯甲硫醇和磺基苯甲胺。分散剂还可以包括无机组分(例如基于硅的组分)。
本发明范围内的合适的聚合物和低聚物包括，但不限于，聚丙烯酸酯、聚苯甲酸乙烯酯、聚硫酸乙烯酯、聚磺酸乙烯酯(包括磺化的苯乙烯)、聚碳酸双酚酯、聚苯并咪唑、聚吡啶、磺化的聚对苯二甲酸乙二醇酯。其它合适的聚合物包括聚乙烯醇、聚乙二醇、聚丙二醇等。
除了分散剂的特征外，控制催化剂悬浮液中分散剂与催化剂原子的摩尔比也是有利的。更有用的考量因素是分散剂官能团和催化剂原子之间的摩尔比。例如，在二价金属离子的情况中，需要两摩尔当量的一价官能团提供理论化学计量比。通常，分散剂官能团与催化剂原子的摩尔比优选约为0.001∶1至50∶1。对于过氧化氢催化剂，该摩尔比优选约为0.5∶1至40∶1，更优选约为1∶1至35∶1，最优选约为3∶1至30∶1。
本发明的分散剂可用于形成非常小且均一的纳米颗粒。通常，在所述分散剂存在下形成的纳米催化剂颗粒的粒度优选小于约20微米。在一些情况中，所述纳米催化剂颗粒可以是原子分散的。纳米催化剂颗粒的平均粒度更优选小于约15纳米，最优选小于约10纳米。
最后，根据纳米催化剂颗粒在载体材料上所需的稳定性，可以对分散剂进行选择，以结合(例如共价结合)载体材料，从而将纳米催化剂颗粒和/或原子固定或限制在载体材料上。虽然分散剂能够在无固定的情况下抑制纳米催化剂颗粒的团聚，但是通过配体使纳米催化剂颗粒结合到载体材料上是特别有效地防止团聚的方法。
用于与载体结合的合适的官能团与适用于与金属离子结合的官能团的类型相同。但是，分散剂分子还可以具有用于与载体结合以及与金属离子结合的不同官能团。
C.溶剂和化学改性剂
在可应用于催化剂载体材料的溶液中制备金属离子。所述溶液可含有各种溶剂，包括水和有机溶剂。溶剂通过向金属离子和分散剂分子的相互作用提供溶液而参与到催化剂的形成中。合适的溶剂包括水、甲醇、乙醇、正丙醇、异丙醇、乙腈、丙酮、四氢呋喃、乙二醇、二甲基甲酰胺、二甲亚砜、二氯甲烷等，包括它们的混合物。
液体混合物中还可包含其它化学改性剂。例如，可以加入酸或碱以调节混合物的pH值。还可以将酸和碱作为固体材料加入。例如，可以使用具有碱性或酸性官能团的离子交换树脂。通过简单的技术如离心和分离容易将固体材料与最终的胶体分离。可以加入表面活性剂，以调节混合物的表面张力，或者稳定纳米颗粒。
D.还原剂
使用还原剂来将金属离子还原到较低的氧化态。
可以使用任何能还原金属离子的化合物。在一个优选的实施方式中，还原剂是氢。其它合适的还原剂包括小有机分子，例如甲醛、甲酸、甲醇、乙烯，以及氢化物，例如氢化铝锂和硼氢化钠。
E.载体材料
将纳米催化剂颗粒沉积和/或形成在载体材料上。载体可以是有机或无机的。载体可以是化学惰性的，或者作为对纳米催化剂的催化作用的补充。载体可以是各种物理形式。载体可以是多孔或无孔的。载体可以是三维结构，例如粉末、颗粒、片材或挤出物。载体可以是两维结构，例如膜、隔膜或涂层。载体可以是一维结构，例如窄纤维。
一类载体材料包括多孔无机材料，例如氧化铝、二氧化硅、二氧化钛、硅藻土(kieselguhr)、硅藻土(diatomaceous earth)、膨润土、粘土、氧化锆、氧化镁、金属氧化物、沸石和碳酸钙。另一类有用的载体包括碳基材料，例如炭黑、活性炭、石墨、氟化碳等。其它载体包括聚合物和其它无机固体、金属和金属合金。
可以将纳米催化剂颗粒以宽范围内的负载量沉积在载体材料上。负载量可以约为0.01重量％-70重量％的负载的纳米催化剂颗粒，更优选约为0.1-25重量％。在载体材料是多孔的情况中，优选表面积至少约为20米2/克，更优选至少约为50米2/克。
III.制备胶体和负载型纳米催化剂的方法
制备本发明的胶体的方法可以广泛地概括如下。首先，选择一种或多种类型的催化金属原子(例如，基态金属或离子化的金属盐形式)和一种或多种类型的分散剂分子(例如羧酸盐形式)。
将金属原子和分散剂分子溶解在溶剂中，进行反应，形成大量络合的金属原子。对溶剂、催化金属原子和分散剂分子进行选择，使得得到的混合物pH至少约为4.25，更优选至少约为4.75，最优选至少约为5.0。在另一个实施方式中，pH的范围约为4.25至7.0，更优选约为5.5-6.0。
在一个优选的实施方式中，金属原子作为溶液中卤盐形式(氯化钯)提供。在此实施方式中，金属卤盐的溶液优选具有低浓度的无机酸，例如HCl。较佳地，金属盐溶液中酸的重量百分含量小于约15％，更优选小于约10％。具有低酸浓度的贵金属的溶液可以制得或商购(例如，含有7％w/w游离酸(例如HCl)的钯溶液可以从科洛尼亚尔金属公司(Colonial Metals Co.)购得)。最大程度地减少催化剂混合物中卤离子的量也是有利的，因为卤素会腐蚀过氧化氢制备中使用的设备。
一旦金属原子与有机试剂络合后，用还原剂还原络合的金属原子，形成大量分散在溶剂中的纳米催化剂颗粒，从而形成胶体。使溶液长时间(例如至少30分钟)接触还原剂，以提高胶体的稳定性，使得胶体的浓度可以更高而不会导致明显的沉淀。在一个优选的实施方式中，还原进行至少1小时，更优选进行至少2小时，最优选进行至少6小时。
与没有通过长时间还原而稳定的胶体相比，本发明最终形成的胶体中的金属的浓度增加。在一个示例性实施方式中，本发明的胶体中金属的最终浓度优选大于约150重量ppm，更优选大于约200重量ppm，最优选大于约300重量ppm。
胶体中金属的浓度是溶剂与金属离子的比例的结果。增加溶剂的量会降低金属浓度，而减少溶剂的量会增加金属浓度。在本发明的方法中，可以通过选择金属与溶剂的初始比例从而提供所需的浓度比值来提供金属浓度，或者在形成纳米颗粒后通过除去一部分溶剂来增加金属与溶剂的比例。这些实施方式的组合也可以实施。
在第一实施方式中，胶体以全浓度(即金属的浓度接近或完全等同于最终的浓度)制备。金属原子、有机分散剂、溶剂和其它组分在合适量的溶剂中混合在一起，使得胶体具有所需的最终金属浓度(例如150重量ppm)。在另一个实施方式中，可以较低的浓度形成胶态颗粒，然后除去(例如通过蒸发)一部分溶剂，以将金属浓度增加到所需的最终浓度。以高浓度制备胶体比在颗粒形成后浓缩胶体更有利，这是因为以全浓度制备胶体避免了浓缩胶体所需的花费。
IV.实施例
以下实施例提供了制备含金属纳米颗粒的浓胶体的配方。使用Pd2+溶液、Pt4+溶液和聚丙烯酸酯溶液制备实施例中的配方。
制备含7.13％(w/w)游离酸(例如HCl)的14.34％(w/w)钯溶液。(该溶液也可以直接从科洛尼亚尔金属公司(Colonial Metals Co.)购得)。将0.2614克H2PtCl6与1000毫升去离子水混合制得0.010重量％的铂溶液。通过用去离子水将15克45重量％的聚丙烯酸钠盐溶液(分子量约为1200)稀释到总重为100克来制备6.75重量％的模板试剂。
实施例1：611ppm浓胶体
实施例1描述了依据本发明的制备金属浓度为611重量ppm的胶体的方法。将2.508克14.34％的钯溶液、72毫升0.010％Pt溶液和60毫升6.75％的聚丙烯酸溶液混合在一起，用去离子水稀释到600毫升。用氮气以100毫升/分钟的流量吹扫溶液2小时，然后用氢气吹扫过夜(大约12小时)。在氢气吹扫约7分钟后，混合物的颜色从深琥珀色转变为深黑色。在混合物的表面上形成薄镜面状的膜，但是继续还原20分钟到1小时内该膜完全消失。在长时间还原后，没有观察到任何沉淀，将胶体静置1个月以上，也没有观察到任何沉淀。胶体的pH值为5.84。
实施例2：1222ppm浓胶体
实施例2描述了依据本发明的制备金属浓度为1222重量ppm的胶体的方法。按照实施例1所述的方法制备实施例2，不同的是将2.508克14.34％的钯溶液、72毫升0.010％Pt溶液和60毫升6.75％的聚丙烯酸溶液混合在一起，用去离子水稀释到300毫升。在长时间还原后，没有观察到任何沉淀，将胶体静置1个月以上，也没有观察到任何沉淀。胶体的pH值为5.77。
本发明在不偏离其精神或主要特征的情况下可以用其它具体形式来实施。所述的实施方式在各方面都可以被认为只是用来说明而不构成限制。因此，本发明的范围由所附权利要求书而不是前面的描述来表明。在权利要求书的含义和等同范围之内的所有变化都包含在其范围之内。
Claims (28)
1.一种制备浓金属胶体的方法，其包括：
(i)使溶剂、大量金属原子和大量有机试剂分子混合在一起，各有机试剂分子包含至少一个能与所述金属原子结合的官能团；
(ii)使所述金属原子与有机试剂分子反应，形成包含大量络合的金属原子的混合物，该混合物的pH至少约为4.25；和
(iii)使用还原剂使所述混合物中络合的金属原子还原至少0.5小时，在混合物中形成稳定的胶态纳米颗粒。
2.如权利要求1所述的方法，其特征在于，还原进行的时间至少约为1小时。
3.如权利要求1所述的方法，其特征在于，还原进行的时间至少约为6小时。
4.如权利要求1所述的方法，其特征在于，混合物的pH大于约4.75。
5.如权利要求1所述的方法，其特征在于，混合物的pH大于约5.0。
6.如权利要求1所述的方法，其特征在于，所述金属原子作为金属盐提供。
7.如权利要求1所述的方法，其特征在于，所述金属在混合物中的最终浓度大于约150重量ppm。
8.如权利要求1所述的方法，其特征在于，所述最终浓度大于约200重量ppm。
9.如权利要求1所述的方法，其特征在于，所述最终浓度大于约300重量ppm。
10.如权利要求1所述的方法，其特征在于，所述方法还包括除去一部分溶剂以实现最终浓度。
11.如权利要求1所述的方法，其特征在于，所述还原剂是氢气。
12.如权利要求1所述的方法，其特征在于，所述纳米颗粒的粒度小于约10ppm。
13.如权利要求1所述的方法制备的纳米颗粒的胶态悬浮液。
14.一种制备负载型催化剂的方法，其包括将如权利要求1所述的纳米颗粒沉积在催化剂载体材料上。
15.一种如权利要求14所述制备的负载型催化剂。
16.一种制备浓金属胶体的方法，其包括：
(i)使溶剂、大量金属原子和有机聚合物混合在一起，所述有机聚合物包含多个能与金属原子结合的官能团；
(ii)使所述金属原子与有机聚合物反应，形成在pH约为4.25-7.0的混合物中的大量络合的金属原子；和
(iii)使氢气通过混合物一段时间，该时间大于约0.5小时，从而在所述混合物中形成稳定的胶态颗粒。
17.如权利要求16所述的方法，其特征在于，所述氢气通过混合物的时间大于约1.0小时。
18.如权利要求16所述的方法，其特征在于，所述氢气通过混合物的时间大于约6.0小时。
19.如权利要求16所述的方法，其特征在于，所述大量金属原子包括一种或多种选自铂族金属的金属。
20.如权利要求16所述的方法，其特征在于，所述金属原子的浓度大于约150重量ppm。
21.如权利要求16所述的方法，其特征在于，所述金属离子作为含有小于约15％的酸的一种或多种溶液提供，并且基本上不向反应混合物中加入任何其它无机酸。
22.如权利要求16所述的方法，其特征在于，所述金属离子作为含有小于约15％的酸的一种或多种溶液提供，并且基本上不向反应混合物中加入任何其它无机酸。
23.一种制备过氧化氢的方法，其包括使氢气与氧气在如权利要求16所述的方法形成的催化剂存在下反应。
24.一种浓胶体金属组合物，其包含：
溶剂；
大量悬浮液在溶剂中的纳米颗粒，从而形成至少能稳定24小时的胶体组合物，各纳米颗粒包含大量金属原子并具有与至少一部分金属原子结合的有机分散剂分子，其中所述金属原子的浓度大于约150重量ppm。
25.如权利要求24所述的浓胶体金属组合物，其特征在于，所述金属原子的浓度大于约200重量ppm。
26.如权利要求24所述的浓胶体金属组合物，其特征在于，所述金属原子的浓度大于约300重量ppm。
27.如权利要求24所述的浓胶体金属组合物，其特征在于，所述胶体组合物的pH大于约4.25。
28.如权利要求24所述的浓胶体金属组合物，其特征在于，所述胶体组合物的pH大于约5。
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8926937B2 (en) * | 2005-11-14 | 2015-01-06 | Agency For Science, Technology And Research | Highly dispersed metal catalysts |
| EP2060323A1 (en) * | 2007-11-12 | 2009-05-20 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Methods of preparing, optionally supported, ordered intermetallic palladium gallium compounds, the compounds as such, and their use in catalysis |
| FR2924363B1 (fr) * | 2007-11-29 | 2010-10-15 | Inst Francais Du Petrole | Procede de preparation d'un catalyseur de reformage comprenant un support, un metal du groupe viiib et un metal du groupe viib |
| US20100121100A1 (en) * | 2008-11-12 | 2010-05-13 | Daniel Travis Shay | Supported palladium-gold catalysts and preparation of vinyl acetate therewith |
| EP2204249A1 (en) * | 2008-12-16 | 2010-07-07 | Akzo Nobel Coatings International B.V. | Aqueous dispersions of metallic particles |
| JP5322733B2 (ja) * | 2009-03-31 | 2013-10-23 | Ｊｘ日鉱日石エネルギー株式会社 | 一酸化炭素の選択的酸化反応用触媒の製造方法 |
| JP5325037B2 (ja) * | 2009-07-16 | 2013-10-23 | 株式会社ノリタケカンパニーリミテド | 金属ナノ粒子からなる金属材料およびその製造方法 |
| US8507720B2 (en) * | 2010-01-29 | 2013-08-13 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| US8273682B2 (en) * | 2009-12-16 | 2012-09-25 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
| US8329611B2 (en) * | 2009-12-16 | 2012-12-11 | Lyondell Chemical Technology, L,P. | Titania-containing extrudate |
| US8450236B2 (en) * | 2010-04-13 | 2013-05-28 | Cristal Usa Inc. | Supported precious metal catalysts via hydrothermal deposition |
| CA2817595C (en) | 2010-12-20 | 2021-01-05 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
| JP6063681B2 (ja) | 2012-09-19 | 2017-01-18 | 三菱瓦斯化学株式会社 | 金属錯体及び過酸化水素の製造方法 |
| US11731118B2 (en) | 2012-10-10 | 2023-08-22 | Albemarle Catalysts Company B.V. | Supported hydrotreating catalysts having enhanced activity |
| US11633727B2 (en) | 2012-10-10 | 2023-04-25 | Albemarle Catalysts Company B.V. | Supported hydrotreating catalysts having enhanced activity |
| WO2022211218A1 (ko) | 2021-04-02 | 2022-10-06 | 한국과학기술원 | 액체금속 전구체 용액, 이를 이용한 금속막 제조방법 및 이를 포함하는 전자소자 |
Family Cites Families (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148750A (en) | 1977-01-10 | 1979-04-10 | Exxon Research & Engineering Co. | Redispersion of noble metals on supported catalysts |
| JPS5777019A (en) | 1980-10-30 | 1982-05-14 | Toho Rayon Co Ltd | Fibrous activated carbon and its manufacture |
| US4652311A (en) | 1984-05-07 | 1987-03-24 | Shipley Company Inc. | Catalytic metal of reduced particle size |
| US4832938A (en) | 1988-05-13 | 1989-05-23 | E. I. Du Pont De Nemours And Company | Hydrogen peroxide production method using platinum/palladium catalysts |
| US5128114A (en) | 1989-04-14 | 1992-07-07 | E. I. Du Pont De Nemours And Company | Silica microspheres, method of improving attrition resistance |
| US5132099A (en) | 1990-12-27 | 1992-07-21 | Mitsubishi Gas Chemical Company, Inc. | Method for producing hydrogen peroxide |
| US5338531A (en) | 1992-01-21 | 1994-08-16 | Chuang Karl T | Production of hydrogen peroxide |
| US5240893A (en) | 1992-06-05 | 1993-08-31 | General Motors Corporation | Method of preparing metal-heterocarbon-nitrogen catalyst for electrochemical cells |
| US6015485A (en) | 1994-05-13 | 2000-01-18 | Cytec Technology Corporation | High activity catalysts having a bimodal mesopore structure |
| DE4425672A1 (de) | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators |
| DE4443705A1 (de) * | 1994-12-08 | 1996-06-13 | Studiengesellschaft Kohle Mbh | Verfahren zur Herstellung von tensidstabilisierten Mono- und Bimetallkolloiden der Gruppe VIII und Ib des Periodensystems als isolierbare und in hoher Konzentration wasserlösliche Precursor für Katalysatoren |
| US5752976A (en) | 1995-06-23 | 1998-05-19 | Medtronic, Inc. | World wide patient location and data telemetry system for implantable medical devices |
| SE9602484D0 (sv) | 1996-06-24 | 1996-06-24 | Eka Chemicals Ab | Method of producing a chemical compound |
| DE69819385T2 (de) | 1997-03-10 | 2004-09-09 | Japan Science And Technology Corp., Kawaguchi | Herstellungverfahren einer Verbundstruktur bestehend aus metallischen Nanopartikeln umhüllt mit einem organischen Polymer |
| JPH10330103A (ja) | 1997-05-28 | 1998-12-15 | Sumitomo Chem Co Ltd | 過酸化水素の製造方法 |
| DE19745904A1 (de) * | 1997-10-17 | 1999-04-22 | Hoechst Ag | Polymerstabilisierte Metallkolloid-Lösungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren für Brennstoffzellen |
| US6090858A (en) | 1998-03-18 | 2000-07-18 | Georgia Tech Reseach Corporation | Shape control method for nanoparticles for making better and new catalysts |
| AU4100299A (en) * | 1998-05-27 | 1999-12-13 | U.S. Department of Commerce and National Institute of Standa rds and Technology | High nitrogen stainless steel |
| DE19824532A1 (de) | 1998-06-03 | 1999-12-09 | Basf Ag | Verfahren zur Herstellung von Schalenkatalysatoren für die katalytische Gasphasenoxidation von aromatischen Kohlenwasserstoffen und so erhältliche Katalysatoren |
| US6576214B2 (en) | 2000-12-08 | 2003-06-10 | Hydrocarbon Technologies, Inc. | Catalytic direct production of hydrogen peroxide from hydrogen and oxygen feeds |
| US6500968B2 (en) | 1998-08-26 | 2002-12-31 | Hydrocarbon Technologies, Inc. | Process for selective oxidation of organic feedstocks with hydrogen peroxide |
| US6168775B1 (en) | 1998-08-26 | 2001-01-02 | Hydrocarbon Technologies, Inc. | Catalyst and process for direct catalystic production of hydrogen peroxide, (H2O2) |
| DE19915681A1 (de) | 1999-04-07 | 2000-10-12 | Basf Ag | Verfahren zur Herstellung von Platinmetall-Katalysatoren |
| JP4505084B2 (ja) | 1999-09-13 | 2010-07-14 | アイノベックス株式会社 | 金属コロイドの製造方法およびその方法によって製造された金属コロイド |
| IT1318550B1 (it) | 2000-06-01 | 2003-08-27 | Eni Spa | Catalizzatore e processo per la sintesi diretta di acqua ossigenata. |
| IT1318549B1 (it) | 2000-06-01 | 2003-08-27 | Eni Spa | Processo per la produzioni in continuo di acqua ossigenata. |
| US6551960B1 (en) | 2000-06-19 | 2003-04-22 | Canon Kabushiki Kaisha | Preparation of supported nano-sized catalyst particles via a polyol process |
| IT1318682B1 (it) | 2000-08-11 | 2003-08-27 | Enichem Spa | Procedimento integrato per la preparazione di ossidi olefinici. |
| IT1318679B1 (it) | 2000-08-11 | 2003-08-27 | Enichem Spa | Processo per la produzione di acqua ossigenata. |
| US6500969B1 (en) | 2000-12-08 | 2002-12-31 | Hydrocarbon Technologies, Inc. | Integrated hydrogen peroxide production and organic chemical oxidation |
| US6740615B2 (en) | 2000-12-22 | 2004-05-25 | Hydrocarbon Technologies, Inc. | Regeneration of used supported noble metal catalysts |
| US6908873B2 (en) | 2000-12-22 | 2005-06-21 | Headwaters Nanokinetix, Inc. | Regeneration of spent supported metal catalysts |
| US6534661B1 (en) | 2000-12-28 | 2003-03-18 | Hydrocarbon Technologies, Inc. | Integrated process and dual-function catalyst for olefin epoxidation |
| CA2445877C (en) * | 2001-04-30 | 2006-12-19 | Postech Foundation | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
| ITMI20011016A1 (it) | 2001-05-17 | 2002-11-17 | Enichem Spa | Sintesi diretta di acqua ossigenata in un nuovo sitema solvente multicomponente |
| ITMI20011015A1 (it) | 2001-05-17 | 2002-11-17 | Enichem Spa | Sintesi diretta di acqua ossigenata in un sistema solvente multicomponente |
| ITMI20011688A1 (it) | 2001-08-02 | 2003-02-02 | Enichem Spa | Catalizzatore e suo impiego nella sintesi di acqua ossigenata |
| US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
| US6746597B2 (en) | 2002-01-31 | 2004-06-08 | Hydrocarbon Technologies, Inc. | Supported noble metal nanometer catalyst particles containing controlled (111) crystal face exposure |
| US7008607B2 (en) | 2002-10-25 | 2006-03-07 | Basf Aktiengesellschaft | Process for preparing hydrogen peroxide from the elements |
| JP4231307B2 (ja) * | 2003-03-03 | 2009-02-25 | 田中貴金属工業株式会社 | 金属コロイド及び該金属コロイドを原料とする触媒 |
| US7825064B2 (en) * | 2003-06-03 | 2010-11-02 | William Marsh Rice University | Supported catalysts using nanoparticles as the support material |
| US7011807B2 (en) | 2003-07-14 | 2006-03-14 | Headwaters Nanokinetix, Inc. | Supported catalysts having a controlled coordination structure and methods for preparing such catalysts |
| US7713910B2 (en) * | 2004-10-29 | 2010-05-11 | Umicore Ag & Co Kg | Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith |
| US7632775B2 (en) * | 2004-11-17 | 2009-12-15 | Headwaters Technology Innovation, Llc | Multicomponent nanoparticles formed using a dispersing agent |
-
2006
- 2006-03-17 US US11/378,877 patent/US7514476B2/en not_active Expired - Fee Related
-
2007
- 2007-03-13 WO PCT/US2007/063879 patent/WO2007109458A2/en active Application Filing
- 2007-03-13 CN CNA2007800092694A patent/CN101405080A/zh active Pending
- 2007-03-13 JP JP2009501641A patent/JP2009530503A/ja active Pending
- 2007-03-13 EP EP07758431A patent/EP1996326A2/en not_active Withdrawn
- 2007-03-13 KR KR1020087024927A patent/KR101386937B1/ko not_active IP Right Cessation
- 2007-03-16 TW TW096109185A patent/TW200735965A/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW200735965A (en) | 2007-10-01 |
| US20070219084A1 (en) | 2007-09-20 |
| WO2007109458A2 (en) | 2007-09-27 |
| KR20080102306A (ko) | 2008-11-24 |
| KR101386937B1 (ko) | 2014-04-18 |
| EP1996326A2 (en) | 2008-12-03 |
| US7514476B2 (en) | 2009-04-07 |
| JP2009530503A (ja) | 2009-08-27 |
| WO2007109458A3 (en) | 2008-06-26 |
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