CN101918135A - 纳米粒子的担载方法 - Google Patents
纳米粒子的担载方法 Download PDFInfo
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Abstract
本发明提供一种纳米粒子的担载方法,其特征在于,使载体吸附铵根离子,使纳米粒子吸附有机酸,在碱性溶液中使该载体和该纳米粒子接触,由此使该载体吸附该纳米粒子。不管有无超亲水性,都可以将纳米高度分散地担载。
Description
技术领域
本发明涉及使载体担载纳米粒子的方法。
背景技术
以汽车的废气净化用催化剂等的催化剂为代表,已知使催化剂粒子或催化剂辅助粒子等担载于多孔的氧化物之类的具有耐热性且表面积大的载体上的方法。为了确保大的反应表面积以使作为催化剂等的反应效率提高,期待催化剂粒子或催化剂辅助粒子等以纳米水平的微细粒子高度分散地被担载。
例如,日本特开2001-9279号公报中公开了使用以粒径10nm以下的作为催化剂辅助粒子(硫中毒再生用)的氧化钛粒子覆盖氧化铝粒子表面而得到的载体的NOx储存还原型催化剂。并且,作为其制造方法公开了将由氧化铝粒子和氧化钛溶胶构成的浆料的pH设为小于5,然后使pH升高,由此将氧化铝粒子表面用氧化钛微粒覆盖。但在该方法中,如该公报的图10所示,由于在pH上升过程中氧化钛溶胶经过等电点,在此时刻凝聚而立即粗大化。在此时的pH下,氧化铝带电,不会与氧化钛溶胶一起凝聚。如果进一步使pH升高,则氧化钛溶胶凝聚物就开始带负电。但是,由于与凝聚相比再分散需要更长时间,因此氧化钛粒子会在保持凝聚粗大化的状态下吸附在氧化铝粒子上。像这样,在日本特开2001-9279号公报的制造方法中,很可能不是氧化钛微粒覆盖氧化铝粒子表面的状态,而是氧化铝粒子和凝聚的氧化钛粒子简单混合的状态。
另外,在日本特开2004-331444号公报中公开了在含有氧化铝粒子的浆料中加入含钛水溶性有机化合物的水溶液,并进行干燥、煅烧,由此在氧化铝表面担载氧化钛的废气净化用催化剂的制造方法。但是,在这种溶液反应中,形成氧化铝氧化钛复合氧化物而耐热性降低,作为载体的表面积降低,无法维持高度分散地担载氧化钛的纳米粒子的状态。
此外,在日本特开2006-272250号公报中公开了制备用具有羧基的聚合物或具有胺基的聚合物等保护材料覆盖而得到的两种以上的胶体,利用由于在保护材料间作用的亲和力而不同的胶体彼此聚集的情况,从而使粒子排列的方法。但是在该方法中,难以可靠地防止胶体彼此的凝聚,无法稳定地获得纳米粒子被高度分散地担载的状态。
与此相对,本申请人在WO2009/001962中公开了使氧化铝吸附NH4 +离子,利用电位差使超亲水性且吸附了OH-离子的氧化钛吸附、担载于氧化铝上的方法。由此,可以使氧化钛的纳米粒子高度分散地担载在氧化铝粒子的表面上。
即,在上述方法中,在弱碱性溶液中,氧化铝、氧化钛均带负电,但是NH4 +离子仅选择性地吸附在氧化铝上,几乎不吸附在氧化钛上,因此在氧化铝和氧化钛之间产生电位差,利用该电位差在氧化铝表面吸附担载氧化钛纳米粒子。该选择吸附的担载机制基于氧化钛是超亲水性的,因此对OH-离子的吸附强,对NH4 +离子的吸附弱这样的特殊前提而成为可能。
因此,上述的方法是以所担载的氧化钛具有超亲水性为前提而得以实现的方法,具有不适用于其他粒子的限制。
因此,需要一种也能适用于氧化钛以外的纳米粒子的高度分散的担载方法。
发明内容
本发明的目的在于提供一种不管有无超亲水性,都可以将纳米粒子高度分散地担载的方法。
根据本发明,上述目的通过如下纳米粒子的担载方法来实现,其特征在于,使载体吸附铵根离子,使纳米粒子吸附有机酸,在碱性溶液中使该载体和该纳米粒子接触,由此使该载体吸附该纳米粒子。
在碱性溶液中,吸附了铵根离子的载体部分带正电,吸附了有机酸的纳米粒子带很大的负电,因此利用载体和纳米粒子的电位差而在载体上吸附纳米粒子。载体之间、纳米粒子之间由于电位相同,因此不发生凝聚而维持高度分散。
关于载体,典型的是氧化铝,但没有必要限定于此,可以使用迄今为止一直作为废气净化用催化剂等的载体来使用的以氧化锆、氧化钛等为代表通常作为载体来使用的氧化物或复合氧化物。
纳米粒子只要可以吸附有机酸就对其没有特别限定,可以是过渡金属、稀土类元素等的氧化物及其复合氧化物以及与担载相关的表面被氧化了的氮化物、碳化物等。
作为有机酸,可以使用琥珀酸、苹果酸、酒石酸、柠檬酸等多元羧酸。
附图说明
图1是表示在使作为载体的氧化铝粒子吸附铵根离子,使作为纳米粒子的二氧化铈溶胶吸附柠檬酸时,氧化铝粒子和二氧化铈溶胶粒子相对于溶液pH值的ζ电位。
图2模式化地表示氧化铝粒子的表面部分地带正电和二氧化铈溶胶粒子表面带负电。
图3是表示本发明的实施例1采用的担载方法的流程图。
图4是表示本发明的实施例2采用的担载方法的流程图。
具体实施方式
针对使用氧化铝粒子作为载体、使用二氧化铈溶胶作为纳米粒子的典型性情况,对本发明的吸附、担载机制加以说明。
图1表示在使作为载体的氧化铝粒子(平均粒径以微米级计,具有几纳米~几十纳米的中级细孔)吸附铵根离子、使作为纳米粒子(平均粒径:一次粒径5nm左右,凝聚二次粒径10~15nm)的二氧化铈溶胶吸附柠檬酸时,氧化铝粒子和二氧化铈溶胶粒子相对于溶液pH值的ζ电位。
如图所示,在弱碱性侧,氧化铝在0.05mol/L的硝酸铵水溶液中带负电(图中的△制图点),二氧化铈溶胶在柠檬酸铵水溶液中也带负电(图中的▲制图点),这种情况下两者间的电位差对于产生吸附而言是不充分的。
当使硝酸铵水溶液的浓度增加到0.15mol/L时,氧化铝的带电量虽然为负但变得非常小(图中的○制图点),二氧化铈溶胶的带电量不发生变化(▲制图点)。
如图2所示,氧化铝粒子的表面随盐浓度增加对铵根离子的吸附增加,成为部分带正电的状态。图示的氧化铝粒子的表面由于NH4 +而部分地带正电。NH4 +表示的部分以外吸附OH-,整体上带负电。
而二氧化铈粒子的表面吸附柠檬酸,用于吸附以外的羧基一部分解离而作为粒子带负电。在少量的铵根离子的浓度变化时,该负的带电量不变(图1)。另外,在图2中将柠檬酸对二氧化铈溶胶的配位简略化,仅示出COOH-(羧基)。
如此,氧化铝粒子表面由于吸附的铵根离子而部分地带正电,二氧化铈粒子表面由于吸附的柠檬酸之类的有机酸而带负电,利用两者的电位差,在氧化铝粒子表面上选择性地吸附二氧化铈纳米粒子。
此时,虽然两粒子的表面整体带正负电时,有可能使吸附速度过快而损害二氧化铈纳米粒子的分散性,但在氧化铝粒子表面部分地带正电的状态下,可以推定选择性和速度慢对分散性而言起到有利作用。
实施例
[实施例1]
根据本发明,按照下面的顺序和条件,使作为载体的氧化铝粒子担载作为纳米粒子的二氧化铈溶胶。
(1)二氧化铈溶胶的制作
首先在0.5M硝酸铈溶液中添加氨水,使pH为6,得到沉淀,分离水分。
接着,添加到0.5M柠檬酸溶液中使其分散,加入氨水使pH为8,得到均匀的纳米粒子分散胶体。
得到的二氧化铈纳米粒子的凝聚二次粒径为10~15nm,一次粒径为5nm左右。
(2)向活性氧化铝的吸附
使经上述制成的二氧化钛溶胶按照图3中示出的流程图的顺序吸附在活性氧化铝上。
这里,使Ce/Al=5/100(原子比)。
首先,将0.15M硝酸铵水溶液调整为pH8。向其中添加干燥活性氧化铝1kg,并搅拌,进行粉体细孔的脱气。经过大约30分钟后,每次适量地缓慢添加上述得到的中性二氧化铈溶胶500g,用约5分钟添加总量。然后,继续搅拌约1h。过滤,进行1次水洗,在120℃干燥过夜。然后,在800℃煅烧2h。由煅烧后的重量可以确认几乎担载了全部量的二氧化铈溶胶。
[比较例1]
将已干燥的活性氧化铝添加到蒸馏水中,搅拌后进行过滤,测定重量而求出给水率。接着,准备预先备好的硝酸铈水溶液。向干燥氧化铝粉末给与硝酸铈水溶液,以使此时的浓度基于上述给水率达到Ce/Al=5/100(原子比)。然后过滤,在80℃干燥后,在800℃煅烧2h。二氧化铈(CeO2)担载量为Ce/Al=5/100(原子比)。
[现有例1]
混合硝酸铈和硝酸铝,以使Ce/Al=5/100(原子比),准备以总金属计为0.5M的水溶液。接着,边搅拌上述水溶液,边较快速地滴加氨水,使pH为6.5。接着,继续搅拌2h后,进一步滴加氨水使pH为7.8。然后,继续缓慢搅拌1h。然后,过滤并在80℃干燥过夜,在大气中在800℃煅烧2h。
表1汇总示出实施例1、比较例、现有例中得到的样品的表面积的实测值。
表1
表1 载体的表面积(800℃,煅烧2h时)
表面积载体种类 (m2/g) | |
二氧化铈 352 | |
现有例1 | 二氧化铈氧化铝复合氧化物 1150 |
比较例1 | 活性氧化铝+硝酸铈吸水※ 1452 |
实施例1 | 活性氧化铝+二氧化铈微粒粒子吸附※ 1723 |
活性氧化铝 1805 |
※Ce/Al原子比=5/100
可知实施例1尽管添加了与比较例等量的Ce,但与比较例相比表面积大,可以减小在800℃煅烧时的表面积降低。
现有例是Ce离子和Al离子互相混杂的状态,推测未获得氧化铝本来的高耐热性,在耐热性相对较低的二氧化铈铝酸盐化的部分,表面积的降低大。
对于比较例,可以认为Ce离子向活性氧化铝晶界被浓缩,二氧化铈铝酸盐在晶界生成,结果是氧化铝的粒子发生再排列,而表面积降低。
与此相对,实施例1由于氧化铝的骨架和晶界被维持在初期状态,且是在氧化铝粒子的表面吸附、担载有二氧化铈纳米粒子的状态,其结果是几乎没有表面积的降低。从数据上可以推测,二氧化铈的密度7.2g/cm3大于活性氧化铝的密度3.78g/cm3,因此表面积稍稍降低。
[实施例2]
按照下述的顺序制作二氧化铈溶胶(胶体)。
首先,在0.5M硝酸铈溶液中添加氨水,使pH为6,得到沉淀,分离水分。
接着,添加到0.8M苹果酸溶液中使其分散,加入氨水使pH为8,得到均匀的纳米粒子分散胶体。
以下与实施例1同样地搅拌1小时,使活性氧化铝吸附二氧化铈溶胶。对吸附后的液体的激光散射进行了测定,但未观察到因纳米粒子而产生的散射。
之后,进一步继续搅拌1小时。过滤,在120℃干燥过夜。然后,在800℃煅烧2h。从煅烧后的重量可以确认几乎担载了全部量的二氧化铈溶胶。
可以在pH值一定且对铵根离子没有影响,不损害二氧化铈溶胶的分散的情况下吸附在氧化铝载体上。
[实施例3]
在本实施例中,将氧化铁纳米粒子担载在氧化铝载体上。
氧化铁溶胶(胶体)按照下述顺序制成。
首先,在0.5M硝酸亚铁溶液中添加氨水,使pH为8,得到沉淀,分离水分。
接着,添加到0.5M柠檬酸中使其分散,加入氨水使pH为8,得到均匀的纳米粒子分散胶体。
得到的氧化铁纳米粒子的凝聚二次粒径为10~15nm,一次粒径为5nm左右。
以下,进行与实施例1同样的操作,使氧化铁纳米粒子吸附在活性氧化铝载体上。对吸附后的液体的激光散射进行了测定,但未观察到因纳米粒子而产生的散射。
根据本发明,提供一种不管有无超亲水性,都高度分散地担载纳米粒子的方法。
本发明的方法对于以汽车用废气净化用催化剂为代表的用于太阳能转换的催化剂等各种催化剂是有用的。该技术可以产生以往未实现的高速反应,对于今后的能量革命而言是一种必不可少的技术。
Claims (3)
1.一种纳米粒子的担载方法,其特征在于,使载体吸附铵根离子,使纳米粒子吸附有机酸,在碱性溶液中使该载体和该纳米粒子接触,由此使该载体吸附该纳米粒子。
2.根据权利要求1所述的方法,其特征在于,所述有机酸是多元羧酸。
3.根据权利要求1或2所述的方法,其特征在于,所述载体是氧化铝。
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