CN107876796B - 一种氨分解制氢钌基催化剂及其制备方法 - Google Patents
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Abstract
本发明属于纳米催化材料技术领域，特别涉及一种碳纳米管担载纳米钌基催化剂的制备方法。本发明所要解决的技术问题是提供一种制备碳纳米管担载均一尺寸纳米钌基催化剂的制备方法。该催化剂制备方法主要涉及两步：第一步，纳米钌胶体颗粒制备，主要采用长链有机胺作为溶剂和还原剂在一定温度和无氧条件下，将金属钌盐原位还原为金属钌；第二步，将纳米金属钌胶体溶液浸渍到碳纳米管载体表面。该催化剂由活性组分钌和碳纳米管载体组成。本发明提供的碳纳米管担载纳米钌基催化剂的制备方法简单可控，催化剂活性组分分散性好，并且氨分解催化活性高。
Description
技术领域
本发明属于纳米催化材料技术领域，特别涉及一种氨分解制氢用碳纳米管担载纳米钌基催化剂及其制备方法。
技术背景
碳纳米管是一种典型的碳纳米材料，同时也是一种很有潜力的催化剂载体，具有较好的传导性、高的热稳定性、较高的比表面积和孔道结构以及良好的导热和电子传导性能。但由于其表面金属锚定位数量有限，不利于研制高分散的担载型金属催化剂。
近些年来基于胶体化学相关理论技术的发展，在纳米颗粒的合成上取得了许多进展，使得纳米金属颗粒尺寸和形貌在液相调控成为可能。采用液相还原反应，可以获得尺寸均一的钌纳米晶胶体溶液，避免以往常规合成的纳米颗粒尺寸分布不均匀，稳定性差，容易团聚等特点。另外，采用有机胺体系制备钌纳米晶胶体溶液，一方面避免了有毒性还原剂的使用，另一方面，制备出的钌纳米晶亲油性较好，颗粒不易团聚，纳米晶表面的有机物配体更容易去除，更易分散在正己烷当中。
鉴于常规浸渍法制备碳纳米管担载金属催化剂可能存在金属颗粒尺寸不均等缺点，采用液相还原法制备活性金属钌纳米胶体溶液并担载在碳纳米管载体上，所制备的碳纳米管担载的纳米钌基催化剂活性组分分散性好，比表面积大，在氨分解反应中能提供更多的活性位点以降低催化反应的活化能，有较高的活性和稳定性，因此在非均相催化反应中具有巨大的应用前景。
发明内容
本发明所要解决的技术问题是提供一种氨分解制氢纳米钌基催化剂的制备方法，由活性组分和碳纳米管载体组成，活性组分为钌纳米颗粒，采用长链有机胺作为溶剂和还原剂，将钌的盐溶液还原为钌纳米金属并以该形式存在于催化剂中。本发明提供的碳纳米管担载纳米钌基催化剂的制备方法简单可控，催化剂活性组分分散性好，颗粒尺寸均一，并且在氨分解制氢反应中催化活性高，稳定性好。
本发明的技术方案：
本发明提供了一种氨分解制氢纳米钌基催化剂，由长链有机胺液相还原所制备的钌纳米胶体溶液浸渍到碳纳米管载体表面而成。
本发明提供的上述氨分解制氢纳米钌基催化剂的制备方法主要涉及两步：第一步，纳米钌胶体颗粒制备，主要采用长链有机胺作为溶剂和还原剂在一定温度和无氧条件下，将金属钌盐原位还原为金属钌；第二步，将纳米金属钌胶体溶液浸渍到碳纳米管载体表面。具体如下：
1)将0.0365mol有机胺加入50mL三口烧瓶中，Ar气氛保护下加热至65℃；将0.20mmol RuCl3·3H2O粉末加入烧瓶中，搅拌溶解，磁力搅拌下将温度升至110℃，停留20min，除去体系中的水分及空气；将温度升至260℃，在此温度下磁力搅拌并停留反应20min；将反应后的溶液降至65℃，加入乙醇和正己烷溶液，离心(10000r/min，5min)，重复上述步骤清洗产品数次后，将所得的黑色固体粉末分散在非极性的正己烷中；
2)将1g碳纳米管载体分散在20mL正己烷中并超声分散1h(功率：100％)，取2wt％计量数的Ru纳米晶分散在15mL正己烷中，超声分散30min(功率：100％)；将该Ru纳米晶溶液逐滴加入碳载体正己烷溶液中，超声分散1h(功率：100％)，室温搅拌12h，将搅拌后的悬浊液离心分离(5000r/min，3min)，得到的下层固体在60℃干燥箱中干燥12h，即得到本发明的碳纳米管担载纳米钌基催化剂。
本方法活性组分的制备为胺类液相还原反应，采用十二烷胺、十四烷胺等长链有机胺作为溶剂和还原剂，不同胺类还原得到不同均一尺寸的钌纳米晶。
本发明具有以下有益效果：
本发明催化剂活性金属钌的制备过程中，采用长链有机胺作为溶剂和还原剂，制备方法简单可控，不仅避免了有毒性还原剂的使用，且所制备的钌纳米晶亲油性较好，钌纳米晶表面的有机配体能够有效阻止钌纳米颗粒的团聚，易分散在正己烷中；采用浸渍方法即可将钌纳米颗粒担载在碳纳米管上，活性组分分散性好，比表面积大，活性位点多。
本发明所制备的碳纳米管担载的纳米钌基催化剂催化活性高，稳定性好，在氨分解反应中具有优异的催化性能。
附图说明
图1是本发明的工艺流程图。
图2(a)和图2(b)是实施例3制备的Ru/CNs催化剂钌纳米晶和将钌纳米晶担载在碳纳米管上的催化剂的透射电镜图。由图可知，通过液相还原法制备的钌纳米晶整体呈现蠕虫状颗粒，颗粒尺寸均一，担载后的钌纳米晶均匀分布在碳纳米管上。
图3是碳纳米管担载不同有机胺类还原的钌纳米晶的氨分解转化率图。结果表明，硬脂胺体系催化剂氨分解的转化率最高，450℃转化率达89.44％，500℃时接近完全转化。催化剂具有较高的氨分解催化活性。
具体实施方式
实施例1：
将0.0365mol十二胺加入50mL三口烧瓶中，Ar气氛保护下加热至65℃形成澄清透明的淡黄色液体。然后，将0.20mmol RuCl3·3H2O粉末加入烧瓶中，搅拌溶解形成墨绿色溶液。磁力搅拌下将温度升至110℃，停留20min，除去体系中的水分及空气。此时，溶液由墨绿色转变为澄清透明的棕红色液体。随后，将温度升至260℃，在此温度下磁力搅拌并停留反应20min后，得到黑色溶液。将反应后的溶液降至65℃，加入乙醇溶液，离心(10000r/min，5min)，再加入乙醇和正己烷的混合溶液清洗产品数次后，将所得的黑色固体粉末分散在非极性的正己烷中。取1g碳纳米管载体分散在20mL正己烷中，超声分散1h(功率：100％)，取2wt％计量数的十二胺还原的Ru纳米晶分散在15mL正己烷中，超声分散30min(功率：100％)。然后，将该Ru纳米晶溶液逐滴加入碳载体正己烷溶液中，超声分散1h(功率：100％)，室温搅拌12h，将搅拌后的悬浊液离心分离(5000r/min，3min)，得到的下层固体在60℃干燥箱中干燥12h，制得碳纳米管负载的纳米钌基催化剂。
实施例2-5：
与实施例1相比仅制备钌纳米晶所用的还原剂长链有机胺不同，其它过程与实施例1相同，制得各成品催化剂。实施例2至实施例5的催化剂组成如表1所示。
表1催化剂组成表
综上可知，本发明催化剂的制备，首先采用液相还原反应将活性金属钌的盐溶液还原为金属钌纳米颗粒，再将其负载于载体上，提高了活性金属钌在载体上的分散度，防止催化剂在制备过程中发生团聚以及在后续催化反应中出现的高温烧结，避免催化剂失活。活性金属制备过程采用有机胺作为还原剂，避免了有毒性还原剂的使用，且采用简单的液相还原反应，使制备过程更易控制和实现。将活性金属通过浸渍法担载在碳纳米管载体上，活性金属用量少，制备成本低，活性金属分散性好，活性位点多。将本发明所制备的催化剂用于氨分解制氢反应，催化反应活性高，稳定性好。
Claims (2)
1.钌纳米晶的制备方法，其特征在于：利用长链有机胺做溶剂和还原剂，将活性组分盐溶液还原为钌纳米晶，其具体制备主要经过以下步骤：
1)将0.0365mol长链有机胺加入50mL三口烧瓶中，Ar气氛保护下加热至65℃；
2)将0.20mmol RuCl3·3H2O粉末加入烧瓶中，搅拌溶解，磁力搅拌下将温度升至110℃，停留20min，除去体系中的水分及空气；
3)将温度升至260℃，在此温度下磁力搅拌并停留反应20min；
4)将反应后的溶液降至65℃，加入乙醇和正己烷溶液，离心10000r/min，5min，重复上述步骤清洗产品数次后，将所得的黑色固体粉末分散在非极性的正己烷中；
所述长链有机胺为十二烷胺、十四烷胺、十六烷胺或硬脂胺。
2.权利要求1所述制备方法制备的钌纳米晶制备碳纳米管担载纳米钌基催化剂的方法，其特征是：将1g碳纳米管载体分散在20mL正己烷中并超声分散1h，取2wt％计量数的Ru纳米晶分散在15mL正己烷中，超声分散30min；将该Ru纳米晶溶液逐滴加入碳载体正己烷溶液中，超声分散1h，室温搅拌12h，将搅拌后的悬浊液离心分离5000r/min，3min，得到的下层固体在60℃干燥箱中干燥12h，即得到碳纳米管担载纳米钌基催化剂。
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| CN102974365A (zh) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | 负载型高分散多组份贵金属纳米颗粒催化剂的制备方法 |
| CN105522168A (zh) * | 2016-01-08 | 2016-04-27 | 浙江大学 | 一种立方体铂钌核壳纳米晶的制备方法及其产物 |
| CN105945301A (zh) * | 2016-05-10 | 2016-09-21 | 江南大学 | 一种温和条件下不同粒径金属钌纳米粒子的可控合成方法 |
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| CN101024495A (zh) * | 2006-02-23 | 2007-08-29 | 三星Sdi株式会社 | 碳纳米管、含它的担载催化剂及采用该催化剂的燃料电池 |
| CN102974365A (zh) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | 负载型高分散多组份贵金属纳米颗粒催化剂的制备方法 |
| CN105522168A (zh) * | 2016-01-08 | 2016-04-27 | 浙江大学 | 一种立方体铂钌核壳纳米晶的制备方法及其产物 |
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