CN1964786A - 催化剂的制备方法 - Google Patents
催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及将金属原子担载在表面导入硫醇基的载体上的催化剂的制备方法。该催化剂用作燃料电池的催化剂电极或电容器·二次电池的复合电极以及有机合成用催化剂或环境净化用催化剂等。
Description
技术领域
本发明涉及催化剂的制备方法。更详细地说,涉及用于燃料电池的催化剂电极或电容器·二次电池的复合电极以及有机合成用催化剂或环境净化用催化剂等的催化剂的制备方法。
背景技术
催化反应是主要在催化剂的表面发生的反应,催化活性由该催化剂的表面积决定,因此必需用载体使催化剂高分散化。
将催化剂分散为高分散状态的方法分为以下2种方法:改善催化剂粒子的制备方法的方法(参照例如专利文献1)和将载体表面改性的方法(参照例如专利文献2)。对于前述改善催化剂粒子的制备方法的方法,报道了用于使金属微粒高分散化的化学方法、物理方法等。另外,对于前述将载体表面改性的方法,已知通过氧化处理增大表面积的方法、制造新结构的碳载体的方法等。
但是,至今已经尝试了用多种方法将催化剂以高分散状态分散在载体表面,但是还没有开发出具有期望的分散特性的催化剂。其原因是金属微粒在载体上发生凝集。
因此,为了阻止这种凝集,提出了在制造金属微粒时使用保护材料的方案,但是该保护材料在催化反应时起催化阻碍因素的作用,虽然具有良好的分散特性,却有作为催化剂的功能不足的缺点。
另一方面,使用表面积大的载体时,虽然可得到良好的分散特性,但是由于金属微粒担载在细孔中,有作为催化剂的功能降低的缺点。
专利文献1:特开2003-147642号公报
专利文献2:特开2003-261312号公报
发明内容
本发明是鉴于上述现有技术进行的,目的在于提供一种催化剂的制备方法,其阻止金属微粒在催化剂的载体上的凝集,金属微粒以高分散状态担载在催化剂的载体上。
本发明涉及一种催化剂的制备方法,其特征在于,将金属原子担载在表面导入硫醇基的载体上。
发明效果
根据本发明的制备方法,可提供一种催化剂,其阻止金属微粒在催化剂载体上的凝集,且金属微粒以高分散状态担载在催化剂的载体上。
附图说明
图1本发明的实施例1中得到的催化剂的TEM照片。
图2本发明的实施例2中得到的催化剂的TEM照片。
图3本发明的实施例3中得到的催化剂的TEM照片。
图4本发明的实施例4中得到的催化剂的TEM照片。
图5表示现有技术的比较例1得到的催化剂的TEM照片。
图6实验例1中的氧还原反应性的评价结果的图。
具体实施方式
以往,在用液态还原法将催化剂担载在载体上时,例如,用碳载体等载体时,通过使催化剂前体还原而担载在载体上,此时不能充分阻止催化剂的凝集,因此不能将催化剂以高分散状态担载在载体上。
但是,按照本发明的制造方法,由于使用硫醇化的载体,通过催化剂前体的还原而担载时,硫醇基强力地吸附在金属微粒的表面,因此有效地阻止了金属微粒的凝集,从而得到金属微粒以高分散状态分散在其表面的催化剂。
根据本发明的制备方法,得到这种金属微粒以高分散状态存在于其表面的催化剂,这可能是由于硫醇基具有容易吸附金属,特别是贵金属的性质。
作为本发明所用的载体,可列举例如碳载体、氧化物载体等,这些载体均可适用于本发明。其中,更优选碳载体。
作为碳载体,只要是一般使用的即可,没有特别限制。作为碳载体的具体例子,可列举多层碳纳米管(MWNT)、单层碳纳米管(SWNT)、碳纳米纤维(CNF)、碳黑(CB)、活性炭(AC)、活性炭纳米纤维(ACF)等,但本发明并不限于这些例子。
另外,对于氧化物载体,只要是一般用于催化剂的即可,没有特别限制。作为氧化物载体的具体例子,可列举二氧化硅、氧化铝、沸石等无机氧化物,但本发明并不限于这些例子。
对载体的大小和形状没有特别限制,优选根据催化剂的用途等进行适当选择。
载体的表面例如可如下导入硫醇基。
首先,对载体实施氧化处理。氧化处理是下一工序将载体表面卤化的前处理。
载体的氧化处理可如下进行,即,例如对载体实施酸处理、或通过将载体在空气中等存在氧的气氛中加热,将其表面氧化。
对载体实施酸处理时,例如可使用硫酸、硝酸、盐酸等无机酸;苯磺酸等有机酸;高锰酸钾、过氧化氢、铬酸钾、二氧化铅、氧化铜等氧化剂,这些可分别单独使用,也可以将2种或以上并用。其中,优选硫酸、硝酸、盐酸等无机酸和高锰酸钾。
在提高酸处理的效率的同时,考虑到安全性,对载体实施酸处理时的温度通常优选为300~700℃,更优选为400~500℃。
另外,酸处理所需的时间因载体的种类、酸处理的处理温度等而不同,不能一概而论,但通常在2小时以内。
另一方面,氧化载体表面时,将载体在空气中等存在氧气的氛围气中加热即可。载体的加热温度因载体的材质等而不同,不能一概而论,但例如载体为碳载体时,通常优选为300~700℃,更优选为400~500℃左右。这样,通过将载体在空气中在规定的温度下加热规定的时间(通常为12小时以内),可在载体表面导入羧基。
对载体实施氧化处理后,将该载体表面卤化。载体表面的卤化可使用卤化剂。
作为卤化剂,可列举例如亚硫酰氯、氯化铝、氯化汞等,但本发明不限于这些例子。
载体表面的卤化例如可用卤化剂将载体和卤化剂在适当的温度和时间下搅拌而进行。卤化时的温度通常可以为50~100℃左右。另外,对卤化所需的时间没有特别限制,通常可以在12小时以内。
接着,通过将卤化的载体表面硫醇化导入硫醇基。
对将卤化的载体表面硫醇化的方法没有特别限制。所述方法有有机化学方法、机械化学方法等。
作为有机化学方法的代表例,可列举使卤化的载体和硫醇化剂反应的方法等。
作为硫醇化剂的代表例,可列举氨基甲硫醇、氨基乙硫醇、氨基十二烷硫醇等碳原子数为1~12的氨基烷硫醇;巯基甲醇、巯基乙醇、巯基十二烷醇等碳原子数为1~12的巯基醇;氨基苯硫酚、巯基苯酚等苯衍生物等,但本发明不限于这些例子。
卤化的载体和硫醇化剂的反应例如可通过使两者接触进行。此时,从反应效率的角度考虑,反应温度优选为50~100℃左右。另外,反应时间因反应温度等反应条件等而不同,不能一概而论,但通常在24小时以内。
这样,可得到表面导入硫醇基的载体。接着将金属微粒担载在所得载体上。
用于金属微粒的金属只要是具有催化活性的金属即可,本发明不受其种类的限定。作为该金属的代表例子,以金、铂等贵金属为代表,还可以列举铁、钴、镍、铬、钼、钌等具有电催化剂活性的金属等,这些金属可以分别单独使用,也可以作为合金使用。
作为将金属微粒担载在载体上的方法,例如可列举通过将金属前体用液态还原法还原而担载的方法等。作为其的一个例子,例如可列举以下方法:使用铂作为金属时,用氯铂酸作为铂前体,通过施用超声波、或者进行搅拌等,使表面导入硫醇基的载体与氯铂酸充分接触后,用还原剂还原,从而可将铂担载在载体上。
作为还原剂,可列举例如硼氢化钠、氢化锂铝、氢等,但本发明不限于这些例子。还原剂的量通常相对于金属前体是过量的,例如,优选调整为每1mol金属前体1.5~10mol的量。
这样得到金属原子担载在表面导入硫醇基的载体上的催化剂。金属微粒在该催化剂表面不凝集,金属微粒以高分散状态担载。
对担载在催化剂表面的金属微粒的粒径没有特别限定,但通常为1-3nm左右。另外,催化剂中金属微粒的附着量因存在于载体表面的硫醇基的个数等而不同,但从催化活性等方面考虑,通常优选为载体的10~60%(质量比)左右。催化剂中的金属微粒的附着量例如可通过调整导入载体表面的硫醇基的个数、或者调整金属微粒的附着量来容易地调节。
另外,可根据催化剂所要求具有的性质控制金属微粒的粒径。作为金属微粒的粒径,可通过对担载了金属微粒的催化剂进行热处理来控制。例如,在对担载金属微粒的催化剂进行热处理时,除去载体(例如碳纳米管等)表面的硫醇基,此时邻接的金属微粒之间一体化,因此可将其大小控制得非常均匀。担载金属微粒的催化剂的热处理例如可如下进行,即在150-350℃、优选在200~300℃、更优选在250℃左右的温度下,在氢氛围气中加热2小时以内、优选5~40分钟、更优选10~30分钟、进一步优选15~25分钟。这样,通过调整对担载了金属微粒的催化剂实施热处理时的加热温度和加热时间,可调节担载在催化剂上的金属微粒的粒径。
如上所述,根据本发明的制备方法,使用硫醇化的载体,由于硫醇基强力吸附金属微粒,阻止了金属微粒在催化剂载体上的凝集,可制造金属微粒在催化剂的载体上以高分散状态担载的催化剂。
根据本发明的制备方法得到的催化剂,由于金属微粒在其表面以高分散状态存在,因此例如可适用于燃料电池的催化剂电极或电容器·二次电池的复合电极等。
实施例
以下根据实施例更详细地说明本发明,但本发明并不限于这些实施例。
实施例1
在70℃下将多层碳纳米管100mg在6M硝酸中进行1小、时氧化处理,然后向该多层碳纳米管中加入亚硫酰氯25mL,在70℃下搅拌12小时,由此将多层碳纳米管的表面氯化。
接着,将氯化的多层碳纳米管和氨基乙硫醇在70℃下反应24小时,使多层碳纳米管的表面硫醇化,得到表面导入硫醇基的碳载体。
向得到的碳载体50mg加入10mM氯铂酸水溶液6.4mL,超声波1小时使其分散后,用过量的100mM硼氢化钠水溶液还原,由此得到铂担载在上述碳载体上的催化剂。
将得到的催化剂的透射电子显微镜(以下称为TEM)照片示于图1。要说明的是,比例尺以图1右下方的横线表示,该直线的长度相当于25nm。
由图1所示的照片可知,铂以高分散状态担载在得到的催化剂表面。
实施例2
在500℃下将多层碳纳米管100mg在空气中热处理2小时,然后向该多层碳纳米管中加入亚硫酰氯25mL,在70℃下搅拌12小时,由此将多层碳纳米管的表面氯化。
接着,使氯化的多层碳纳米管和氨基乙硫醇在70℃下反应24小时,使多层碳纳米管的表面硫醇化,得到表面导入硫醇基的碳载体。
向得到的碳载体50mg加入10mM氯铂酸水溶液3.2mL和10mM氯化钌水溶液6.2mL,超声波1小时使其分散后,用过量的100mM硼氢化钠水溶液还原,由此得到铂和钌的合金担载在上述碳载体上的催化剂。
得到的催化剂的TEM照片如图2所示。要说明的是,比例尺以图2右下方的横线表示,该直线的长度相当于25nm。
由图2所示的照片可知,铂和钌的合金粒子以高分散状态担载在得到的催化剂表面。
实施例3
将多层碳纳米管100mg在常温下用97%浓硫酸120mL和70%浓硝酸40mL的混合酸氧化处理1小时,然后向该多层碳纳米管中加入亚硫酰氯25mL,在70℃下搅拌12小时,由此将多层碳纳米管的表面氯化。
接着,将氯化的多层碳纳米管和氨基苯硫酚在70℃下反应36小时,使多层碳纳米管的表面硫醇化,得到表面导入硫醇基的碳载体。
向得到的碳载体25mg加入10mM氯铂酸水溶液3.2mL,超声波1小时使其分散后,用过量的100mM硼氢化钠水溶液还原,由此得到铂担载在上述碳载体上的催化剂。
得到的催化剂的TEM照片如图3所示。要说明的是,比例尺以图3右下方的横线表示,该直线的长度相当于25nm。
由图3所示的照片可知,铂粒子以高分散状态担载在得到的催化剂表面。
实施例4
将碳黑[アメリカ·カ一ボツト(Carbot)社制,商品名:VulcanXC-72R]100mg与1M高锰酸钾水溶液50mL混合,在70℃搅拌1小时,由此进行氧化处理后,向其中加入亚硫酰氯25mL,在70℃搅拌12小时,由此将碳黑表面氯化。
接着,将氯化的碳黑与氨基乙硫醇在70℃反应24小时,将碳黑表面硫醇化,得到表面导八硫醇基的碳载体。
向得到的碳载体100mg加入10mM氮铂酸水溶液12.8mL,超声波1小时使其分散后,用过量的100mM硼氢化钠水溶液还原,由此得到铂担载在上述碳载体上的催化剂。
得到的催化剂的TEM照片如图4所示。要说明的是,比例尺以图4右下方的横线表示,该直线的长度相当于25nm。
由图4所示的照片可知,铂粒子以高分散状态担载在得到的催化剂表面。
实施例5
改变热处理温度,在氢氛围气中对实施例1得到的催化剂实施热处理。首先,在250℃的温度下对催化剂实施热处理,以除去存在于该催化剂上的硫醇基。结果,除去载体表面的硫醇基的同时,金属微粒之间开始一体化,经过10分钟后,粒径为约1nm的金属微粒存在于催化剂表面。接着,将热处理温度变为400℃,与上述同样对催化剂实施热处理,经过10分钟后,粒径约2nm的金属微粒存在于催化剂表面。进一步,将热处理温度变为500℃,与上述同样对催化剂实施热处理,经过10分钟后,粒径约3nm的金属微粒存在于催化剂表面。
由上所述可知,根据实施例5,通过在规定的加热温度下边调整加热时间边对催化剂实施热处理,使金属微粒从最小1nm的粒径开始成长为规定大小的粒径,从而控制得非常均匀。
比较例1
向多层碳纳米管100mg加入10mM氯铂酸水溶液20mg,超声波1小时使其分散后,用过量的100mM硼氢化钠水溶液还原,由此得到铂担载在多层碳纳米管上的催化剂。
得到的催化剂的TEM照片如图5所示。要说明的是,比例尺以图5右下方的横线表示,该直线的长度相当于25nm。
由图5所示的照片可知,铂粒子没有均匀分散在得到的催化剂表面,而是局部凝集。
由各实施例与比较例1的对比结果可知,根据各实施例,可制造以往的方法(比较例1)不能比的程度的阻止了金属微粒在催化剂的载体上凝集,金属微粒以高分散状态吸附在催化剂载体上的催化剂。
实验例1
用实施例5的通过在250℃的热处理温度下实施热处理得到的催化剂(金属微粒的粒径:约1 nm)评价氧还原反应性。
首先,将实施例5得到的催化剂2mg和产ピオン 0.02mL分散在蒸馏水10mL中,将得到的浆液0.01mL涂布于旋转圆盘电极(RDE)用电极(直径3mm,ガラス炭素制)的两面后,使其干燥,制造电极。
用得到的电极,在氧饱和的0.1M高氯酸水溶液中进行循环伏安测量,由此评价氧还原反应性。其结果如图6所示。
由图6所示结果可知,实施例5所得催化剂与普通的担载在纳米管上的铂催化剂相比,氧还原反应的峰沿箭头方向位移,还原反应在氧化更强的方向发生。因此,由该方法制造的催化剂具有大小控制得非常均匀的金属微粒,因此具有稳定的高催化活性。
产业实用性
用本发明的制备方法得到的催化剂例如可适用于燃料电池的催化剂电极或电容器·二次电池的复合电极以及有机合成用催化剂或环境净化用催化剂等。
Claims (4)
1.催化剂的制备方法,其中,将金属原子担载在表面导入硫醇基的载体上。
2.权利要求1所述的催化剂的制备方法,其中载体为碳载体或氧化物载体。
3.权利要求1或2所述的催化剂的制备方法,其中进一步除去存在于载体上的硫醇基。
4.催化剂,其是由权利要求1~3中任意一项所述的催化剂的制备方法制备的。
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GB0021301D0 (en) * | 2000-08-30 | 2000-10-18 | Borealis Tech Oy | Supported catalyst |
JP2002208768A (ja) * | 2001-01-12 | 2002-07-26 | Hitachi Ltd | ポリイミド基体への金属メッキ膜形成方法 |
DE10105104A1 (de) * | 2001-02-05 | 2002-08-08 | Bayer Ag | Verfahren zur Herstellung von nicht-chiralen und optisch aktiven Hydroxygruppen enthaltenden organischen Verbindungen |
EP1570539A2 (en) * | 2002-10-31 | 2005-09-07 | Carbon Nanotechnologies, Inc. | Fuel cell electrode comprising carbon nanotubes |
JP2005087989A (ja) * | 2003-08-08 | 2005-04-07 | Hitachi Ltd | 触媒材料及びその作製方法とそれを用いた燃料電池 |
-
2005
- 2005-03-31 KR KR1020077000610A patent/KR20070028528A/ko not_active Application Discontinuation
- 2005-03-31 US US11/628,972 patent/US20080200329A1/en not_active Abandoned
- 2005-03-31 CA CA002569521A patent/CA2569521A1/en not_active Abandoned
- 2005-03-31 CN CNA2005800187568A patent/CN1964786A/zh active Pending
- 2005-03-31 JP JP2006514418A patent/JP4182231B2/ja active Active
- 2005-03-31 WO PCT/JP2005/006344 patent/WO2005120708A1/ja active Application Filing
- 2005-03-31 EP EP05728021A patent/EP1772190A4/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105482510A (zh) * | 2015-12-20 | 2016-04-13 | 高大元 | 一种纳米伊利石载铂塑料抗菌剂的制备方法 |
CN114361488A (zh) * | 2021-12-23 | 2022-04-15 | 深圳市氢瑞燃料电池科技有限公司 | 一种铂基催化层及其制备方法与应用 |
Also Published As
Publication number | Publication date |
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WO2005120708A1 (ja) | 2005-12-22 |
KR20070028528A (ko) | 2007-03-12 |
EP1772190A4 (en) | 2007-10-10 |
JP4182231B2 (ja) | 2008-11-19 |
US20080200329A1 (en) | 2008-08-21 |
EP1772190A1 (en) | 2007-04-11 |
JPWO2005120708A1 (ja) | 2008-04-03 |
CA2569521A1 (en) | 2005-12-22 |
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