CN108212189A - 一种微量贵金属修饰的过渡金属催化剂及其制备和应用 - Google Patents
一种微量贵金属修饰的过渡金属催化剂及其制备和应用 Download PDFInfo
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Abstract
本发明涉及制备微量贵金属修饰的过渡金属催化剂的制备方法及其在催化加氢和催化脱氢方面的应用。催化剂通过贵金属前驱体与其他过渡金属进行置换反应制备合成。贵金属包括Pt、Pd、Ru、Rh、Au、Ir、Ag等，过渡金属包括Fe、Co、Ni、Cu、Zn等。其中，贵金属的含量为0.0001％～3％。该催化剂可应用于催化加氢和催化脱氢反应中。
Description
技术领域
本发明涉及催化剂的制备方法及其在催化加氢催化脱氢方面的应用。具体涉及一种微量贵金属修饰的负载型非贵金属催化剂的制备及其在氨硼烷水解脱氢和选择性加氢的应用。
背景技术
随着化石燃料的不断枯竭，“氢能经济”正逐渐到来。其中，氨硼烷(NH3BH3)以其高氢含量(19.6wt.％)、稳定的化学性质成为备受关注的产氢材料之一。其产氢方式一般分为两种，即：热分解放氢和水解放氢。一般来说，热分解放氢会产生杂质气体且反应所需温度较高，操作起来相对水解放氢较为困难。氨硼烷水解在催化剂的存在下，按下式进行：
通常贵金属如Pt、Ru、Pd等表现出较优异的性能，但是贵金属的价格较高，并不适合大规模应用。因此廉价的非贵金属催化剂成为人们关注的热点。如铁、钴、镍等过渡金属，具有储存量高、价格低廉等优势。然而，非贵金属与贵金属活性相差几十倍，因此发展高性能的廉价过渡金属催化剂目前仍然是人们所面临的巨大挑战。
含有可还原性基团的芳香硝基化合物选择性加氢得到功能化苯胺类衍生物在诸多领域都有重要应用，如医药、农药、染料、高分子聚合物等。目前商业的功能化苯胺类产物的制备主要还是采用非催化还原方法，造成严重环境污染。因此急需寻找一种环境友好、高效的替代方法。通过负载型金属催化剂进行催化加氢是一个很好的选择。然而，当反应物分子中含有可还原性基团时，选择性地将硝基加氢而保留其他还原性基团不变仍是一项较大的挑战。同样，贵金属催化剂，如：Au、Pt等，在选择加氢中展现出优异地性能。然而贵金属的价格昂贵，并不适合工业化应用。
因此本发明制备了微量贵金属修饰的过渡金属催化剂，并且应用于氨硼烷的水解脱氢和选择性加氢的反应中，大大提高了非贵金属的活性，实现了高效产氢及高选择性加氢的目的。
发明内容
本发明一方面针对现有技术状况，提供一种制备微量贵金属修饰的过渡金属催化剂的方法，提高了催化剂中贵金属的利用率，从而降低催化剂的成本。同时提供了一种用于氨硼烷水解脱氢反应及含有可还原性基团的芳香硝基化合物选择性加氢的低成本催化剂。
为了实现上述目的，采用贵金属与非贵金属结合，制备得到负载型微量贵金属修饰的过渡金属催化剂，合理调变控制条件，可以得到贵金属与其他金属形成合金、或形成壳核结构、或贵金属分布在催化剂表面的结构。
在双金属活性组分中，以载体总重计，微量贵金属占载体的重量百分比为0.0001％～3％，过渡金属的重量百分比为0.1-10％。
本发明中贵金属为Pt、Pd、Ru、Rh、Au、Ir、Ag,其中最好为：Pt、Pd、Au。
本发明中过渡金属为Fe、Co、Ni、Cu、Zn，其中最好为Fe、Co、Ni。
本发明中活性组分过渡金属前驱体为Ni(NO3)2、Co(NO3)2、Fe(NO3)2、Cu(NO3)2、NiCl2、CoCl2、FeCl2、ZnCl2中的一种或两种以上，贵金属前驱体为含贵金属的酸类或盐类如PtCl2、H2PtCl6、Pt(NO3)2、RuCl3、H2PdCl2、HAuCl4、AgNO3、RhCl3、IrCl3中的一种或两种以上。
本发明中催化剂母体制备方法主要包括：浸渍法、共沉淀法、沉积沉淀法等，所用载体包括碳材料、碳氮载体、氧化物载体等常见载体。
本发明中微量贵金属修饰的方法为置换法，其制备方法如下：以过渡金属为催化剂母体，首先将过渡金属催化剂还原到金属状态，然后取一定量过渡金属催化剂分散在溶剂中，在一定温度下向这种悬浊液中加入贵金属前驱体，贵金属前驱体离子会与催化剂母体中金属交换，生成微量贵金属修饰的过渡金属催化剂。
本发明中贵金属前驱体与过渡金属的比例在0.001-0.1之间，交换反应温度为室温至200℃之间，所用溶剂为水、醇类、醚类等常见溶剂。
所制备的微量贵金属修饰的过渡金属催化剂可应用于催化加氢反应，如硝基加氢反应、醛基加氢反应、碳碳双键加氢反应。还可以可应用于催化脱氢反应，如氨硼烷水解脱氢反应。
附图说明
图1.1-1000/CTF催化剂和母体5％Ni/CTF催化剂的X射线衍射图。
图2.1-1000/CTF催化剂的高分辨电镜图。
图3.1000/CTF和母体5％Ni/CTF催化剂氨硼烷水解放氢反应活性对比图。
图4.1-1000/AC和母体5％Ni/AC催化剂氨硼烷水解放氢反应活性对比图。
图5.不同温度下1-1000/CTF催化氨硼烷水解的反应活性对比图。
图6.不同浓度1-1000/CTF催化剂催化氨硼烷水解的反应活性对比图。
具体实施方式
实施例1
Pt与Ni物质的量比为1:1000的催化剂的制备及其在氨硼烷水解脱氢反应中的应用。此实施例中利用碳氮(covalent triazine framework，简称CTF)材料为载体。具体步骤如下：
1.催化剂母体的制备：室温下取500mgCTF材料于烧杯中，用1ml(25mg/ml)Ni(NO3)2溶液浸渍，于室温放置12h，100℃干燥12h，400℃焙烧4h，400℃H2气氛还原4h，得到理论担载量催化剂母体称为5％Ni/CTF，其X射线衍射(XRD)结果如图1所示。
2.微量Pt修饰的5％Ni/CTF的制备，具体为：取100mg步骤1中制得的5％Ni/CTF催化剂于20ml水中，向其中缓慢滴加10ml含0.0165mg的H2PtCl6溶液，搅拌10h，室温干燥，得到理论比例Pt:Ni＝1:1000，得到的催化剂称为1-1000/CTF催化剂，其XRD结果如图1所示。图1中并没有Pt的衍射峰出现，说明Pt以非常小的颗粒存在于双金属催化剂中。从图2的高分辨电镜得知，当Pt-Ni物质的量比例为1-1000时，Pt在Ni纳米颗粒表面以单原子形式存在。
3.1-1000/CTF氨硼烷水解制氢反应的测试：取48mg催化剂于1.5ml水中，向其中注入1ml含有25mg氨硼烷的溶液，室温搅拌，测量放氢体积。
4、同时进行了催化剂母体5％Ni/CTF氨硼烷水解脱氢反应的测试：与步骤3反应条件相同。并与1-1000/CTF催化剂脱氢速率进行对比，如图3所示。图3中可知，微量添加Pt之后的双金属催化剂1-1000/CTF相较于单金属负载型催化剂Ni/CTF，其产氢速度明显加快。
实施例2
Pt与Ni物质的量比为1:1000的催化剂的制备及其在氨硼烷水解放氢反应中的应用。此实施例中利用活性炭(简称为AC)为载体，所合成催化剂标记为1-1000/AC。具体步骤与实施例1中基本相同，只是将碳氮载体换为活性炭载体。由图4可知，微量添加Pt之后的双金属催化剂(1-1000/AC)相较于单金属负载型催化剂Ni，其产氢速度明显加快，提高了2倍以上，说明了此方法修饰在不同载体上过渡金属催化剂都可以提高水解活性。
实施例3
1-1000/CTF催化剂不同温度水解活性评价：与实施例1制备及反应条件相同，依次调变温度，分别在25℃、30℃、35℃、40℃下进行。
由图5可知，提高反应温度，可以提高产氢速率，来满足应用的需求。
实施例4
1-1000/CTF催化剂不同催化剂浓度水解活性评价：与实施例1中反应及制备条件相同，依次调变催化剂浓度，分别在体系中添加6.4mM、9.6mM、12.8mM、16mM催化剂进行反应。
图6可知，加大催化剂的用量，可以提高产氢速率，来满足应用的需求。
实施例5
Pt与Ni物质的量比为1:100的催化剂的制备及其在硝基化合物选择加氢反应中的应用。此实施例中利用碳纳米管(CNT)材料为载体。具体步骤如下：1.催化剂母体的制备：室温下取500mg碳纳米管材料于烧杯中，用1ml
(25mg/ml)Ni(NO3)2溶液浸渍，于室温放置12h，100℃干燥12h，400℃焙烧4h，400℃H2气氛还原4h，得到理论担载量催化剂母体称为5％Ni/CNT。
2.微量Pt修饰的5％Ni/CNT的制备，具体为：取100mg步骤1中制得的5％Ni/CNT催化剂于20ml水中，向其中缓慢滴加10ml含0.165mg的H2PtCl6溶液，搅拌10h，室温干燥，得到理论比例Pt:Ni＝1:100，得到的催化剂称为1-100/CNT催化剂。
3. 1-100/CNT选择性加氢活性评价：取150mg催化剂于30ml的甲醇中，所用加氢底物分别为间硝基苯甲醛、对硝基苯酚、对硝基氯苯，Pt与底物物质的量比例为0.08:1，将其置于不锈钢高压反应釜中。于40℃，3bar的条件下进行加氢。
表1. 1-100/CNT催化不同底物选择性加氢的反应活性及选择性
表1可知，此催化剂还可以应用于选择性加氢的体系中，1-100/CNT在不同含有可还原性基团的芳香硝基化合物上，在温和条件下，均可得到较高的活性及选择性。
Claims (10)
1.一种微量贵金属修饰的过渡金属催化剂，其特征在于：负载型催化剂，活性组份微量贵金属的质量分数为0.0001％～3％，活性组份过渡金属的质量分数为1％～10％，其余为载体；或非负载型催化剂，微量贵金属与过渡金属的物质的量比为1:1000～1:2。
2.按照权利要求1所述的催化剂，其特征在于：贵金属为Pt、Pd、Ru、Rh、Au、Ir、Ag中的一种或二种以上，其中最好为：Pt、Pd、Ru、Au中的一种或二种以上。
3.按照权利要求1所述的催化剂，其特征在于：过渡金属为Fe、Co、Ni、Cu、Zn中的一种或二种以上，其中最好为Fe、Co、Ni中的一种或二种以上。
4.按照权利要求1所述的催化剂，其特征为：贵金属与其他金属形成合金、或形成贵金属包裹过渡金属的壳核结构(Pd@Co，Pt@Ni，Pt@Cu等)、或贵金属分布在非贵金属表面中的一种或二种以上。
5.一种权利要求1-4任一所述的催化剂的制备法方，其特征在于：微量贵金属修饰的方法为置换法，以过渡金属纳米颗粒或负载型过渡金属为催化剂母体，将其分散在溶剂中，浓度为0.005g/ml～0.1g/ml，在室温至200℃的温度下向这种悬浊液中加入贵金属前驱体，贵金属前驱体离子会与母体中金属交换，生成微量贵金属修饰的过渡金属催化剂。
6.按照权利要求5所述的制备方法，其特征在于：贵金属前驱体含贵金属的酸类或盐类如PtCl2、H2PtCl6、Pt(NO3)2、RuCl3、H2PdCl2、HAuCl4、AgNO3、RhCl3、IrCl3中的一种或两种以上。
7.按照权利要求5所述的制备方法，其特征在于：贵金属前驱体与过渡金属的金属物质的量比例在0.001-0.5之间，，所用溶剂为水、醇类、醚类等常见溶剂中的一种或二种以上。
8.按照权利要求5所述的制备方法，其特征在于：过渡金属催化剂为负载型过渡金属催化剂，过渡金属中的一种或二种以上负载于载体上的方法主要包括：浸渍法、共沉淀法、或沉积沉淀法，所用载体包括碳材料、碳氮载体(具体为活性炭、碳纳米管或N掺杂的碳材料)、氧化物载体(具体为氧化铝、氧化钛)等常见载体。
9.一种权利要求1-4任一所述的催化剂的应用，其特征在于：所述的微量贵金属修饰的过渡金属催化剂可应用于催化选择加氢反应中，如硝基加氢反应、醛基加氢反应或碳碳双键加氢反应。
10.按照权利要求9所述的催化剂的应用，其特征在于：微量贵金属修饰的过渡金属催化剂可应用于催化脱氢反应，如氨硼烷水解脱氢反应。
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