CN100435933C - 单层碳纳米突吸附材料的制造方法 - Google Patents
单层碳纳米突吸附材料的制造方法 Download PDFInfo
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Abstract
本发明通过在单层碳纳米突上担载镧族金属，获得具有甲烷吸附性的单层碳纳米突吸附材料，由此提供一种甲烷吸附量大，作为甲烷吸附材料有效的单层碳纳米突吸附材料。
Description
技术领域
本申请的发明涉及单层碳纳米突(carbon nanohorn)吸附材料及其制造方法。更详细地，本申请的发明涉及甲烷吸附量大、作为甲烷吸附材料有效的单层碳纳米突吸附材料及其制造方法。
背景技术
单层碳纳米突具有管状的单层碳纳米管的前端部突起成角(horn)状的圆锥形状，与碳纳米管同样地主要由石墨结构的碳原子面构成。该单层碳纳米突通常是使多个单层碳纳米突的角状前端部朝外，集合成直径为80～100nm左右的球状，制成所谓的大丽花状的碳纳米突集合体，此碳纳米突集合体表面积非常大，容易高纯度地大量合成，所以期待用作重量轻、成本低的吸附材料等(专利文献1(特开2002-159851)和专利文献2(特开2002-326032))。
另一方面，为了解决近年来的能量问题和环境问题，期望将作为天然气原料的甲烷代替媒和石油等燃料，所以提出了各种甲烷的贮藏方法，例如，期待活性炭和活性炭纤维以及高比表面积活性炭等各种碳吸附材料和金属络合物等可以作为甲烷吸附材料。
作为甲烷吸附用的碳类吸附材料，单层碳纳米突(SWNH：singlewalled carbon nanohorn)具有前述特征，SWNH与其它的碳材料相比，可以高密度地吸附甲烷，期待作为优异的甲烷吸附材料，但是目前还略低于实用的目标(美国能源部：35个大气压，150v/v)，或者限于具有相同程度的性能。另外，如图6所示，加热SWNH(图6的□(加热到693K)，与未加热的SWNH(图6中的○(303K))相比，可以增加甲烷的吸附量，在这种情况下，与图6的△(A20：活性炭纤维(303K))或
(AX21：高比表面积活性炭(303K))相比，甲烷吸附量较多，但是◇是(A5：活性炭纤维(303K)并未发现甲烷吸附量有显著的不同，所以需要进一步提高甲烷吸附量。
因此，本申请发明是根据以上事实提出的，课题在于提供可以解决现有技术的问题，甲烷吸附量大，可以贮藏甲烷的新的作为甲烷吸附材料有用的单层碳纳米突吸附材料。
发明内容
本申请的发明作为解决上述课题的方法，首先第1在于提供一种单层碳纳米突吸附材料，其特征在于：在单层碳纳米突上担载镧族金属，从而具有甲烷吸附性。
第2是，本申请的发明提供一种单层碳纳米突吸附材料，其特征在于：相对于每1g单层碳纳米突，镧族金属担载在单层碳纳米突上的担载量为大于等于0.01mmol、小于等于5mmol。
第3是提供一种单层碳纳米突吸附材料，其特征在于：在第1或第2发明中，镧族金属是La、Ce、Pr、Nd、Pm、Sm、Eu、Gd和Tb中的任一种。
第4是提供一种单层碳纳米突吸附材料的制造方法，其特征在于：将单层碳纳米突悬浮于乙醇中，然后加入一定量的硝酸镧族元素的乙醇溶液，再进行超声波处理后，蒸发干燥，将镧族金属担载在单层碳纳米突上。
第5是提供一种单层碳纳米突吸附材料的制造方法，其特征在于：在第4发明中，在将单层碳纳米突悬浮于乙醇中前，加热而在氧气流下氧化。
附图简要说明
图1是表示本申请的发明的单层碳纳米突吸附材料的镧族金属的原子序号导致甲烷吸附密度不同的图。
图2是表示测定本申请的发明的单层碳纳米突吸附材料、通常的单层碳纳米突吸附材料和活性炭纤维的甲烷吸附密度的结果的图。
图3是表示测定本申请的发明的单层碳纳米突吸附材料、通常的单层碳纳米突吸附材料和活性炭纤维以及其它的碳材料的甲烷吸附密度的结果的柱状图。
图4是表示该发明的实施例中的SWNH和Eu/SWNH-ox的甲烷吸附密度的图。
图5是表示该发明的实施例中的SWNH颗粒和Eu/SWNH-ox颗粒的甲烷的吸附量的图。
图6是表示现有的SWNH(加热·非加热)、活性炭纤维、活性炭的甲烷吸附量的图。
具体实施方式
本申请的发明具有上述的特征，在下文中就其实施方式进行说明。
本申请的发明的单层碳纳米突吸附材料的重要的特征在于：在单层碳纳米突上担载镧族金属，具有甲烷吸附性。这种单层碳纳米突吸附材料与通常的单层碳纳米突相比，甲烷吸附量大幅度地增加，特别是，每1g单层碳纳米突，优选担载大于等于0.01mmol、小于等于5mmol的担载量，通过以这种担载量在单层碳纳米突上担载镧族金属，可以进一步提高该单层碳纳米突吸附材料的甲烷吸附量。
此时，使用其它的镧族金属当然也是可以的，特别是作为镧族金属适合选择La、Ce、Pr、Nd、Pm、Sm、Eu、Gd和Tb中的任一种，如图1所示，担载了这些镧族金属的单层碳纳米突吸附材料可以特别高效地吸附甲烷，可以作为极为有用的甲烷吸附材料。另外，图1的横轴表示镧族金属的原子序号，纵轴表示担载了镧族金属的单层碳纳米突吸附材料的甲烷吸附密度。
另外，吸附到担载了镧族金属的单层碳纳米突吸附材料的甲烷，可以仅通过减压而简单且快速地从单层碳纳米突吸附材料脱离。
另外，本申请的发明的单层碳纳米突吸附材料可以通过将单层碳纳米突悬浮于乙醇中，再加入一定量的硝酸镧族元素的乙醇溶液，进行超声波处理后，蒸发干燥，将镧族金属担载在单层碳纳米突上的方法而适当地制造，此外，通过在将单层碳纳米突悬浮于乙醇之前进行加热，在氧气流下氧化，可以增加单层碳纳米突的细孔容量，所以进行加热、氧化，担载了镧族金属的单层碳纳米突与不加热、氧化担载了镧族金属的单层碳纳米突相比，甲烷吸附密度变小，但是整体的甲烷吸附量可能增大。
然后，本申请的发明中的单层碳纳米突(SWNH)通常作为集合体生成，所以镧族金属可以担载在该集和组织体的单层碳纳米突上，也可以担载在各单独的碳纳米突上。
以下，依照附图例示实施例，对本申请的发明的实施方式进行更详细地说明。当然，本发明并不限于以下的例子，对细节方面可以有各种的方式。
实施例
<实施例1>
在惰性气氛气中，对固体状的碳单体物质照射激光，使碳激光蒸发，通过所谓的激光烧蚀法制备单层碳纳米突(SWNH)，将该单层碳纳米突悬浮于乙醇中，然后加入一定量的硝酸镧族元素乙醇溶液，进行5分钟超声波处理后，蒸发干燥，得到担载了镧族金属的单层碳纳米突吸附材料。使用的镧族元素是La、Eu、Er和Lu，担载量分别是每1g的SWNH为0.1mmol。另外，为了比较，根据与上述同样的方法，在活性炭纤维A10上担载进行了同样处理的镧族金属。需说明的是，担载在活性炭纤维A10上的镧族元素是Eu，镧族金属的担载量是每1g的A10为0.1mmol。
在77K下进行氮吸附测定，确认各碳材料的细孔结构，结果如表1所示，几乎没有发现担载镧族金属的细孔容量变化。另外，表面积也几乎没有变化。
表1
| 样品 | 表面积(m<sup>2</sup>g<sup>-1</sup>) | 细孔容量(mLg<sup>-1</sup>) |
| 生长出的SWNH(SWNH as grown) | 310 | 0.11 |
| La/SWNH | 370 | 0.107 |
| Eu/SWNH | 340 | 0.101 |
| Er/SWNH | 350 | 0.101 |
| Lu/SWNH | 350 | 0.108 |
| A10 | 1010 | 0.46 |
| Eu/A10 | 1050 | 0.46 |
接着，在303K、35个大气压下，测定各碳材料的甲烷吸附，结果如图2所示，担载了镧族金属的单层碳纳米突(图2中，黑圈：La/SWNH，黑正方形：Eu/SWNH，黑菱形：Er/SWNH，黑三角形：Lu/SWNH)与未担载镧族金属的单层碳纳米突(图2中的白圈)相比，甲烷吸附密度增加到约1.5倍。特别是，可以知道担载Eu或La的碳纳米突与担载Er或Lu的碳纳米突相比，可以更高效地吸附甲烷。另一方面，A10(图2中的白色倒三角)即使担载了镧族金属(Eu)，也未发现甲烷吸附密度增加的效果(图2中的黑色倒三角)。
另外，在图3的柱状图中，表示SWNH、将SWNH高温氧化形成的物质(图3中的SWNH-ox)、担载了镧族金属的SWNH(图3中的La/SWNH、Eu/SWNH、Er/SWNH、Lu/SWNH)、担载镧族金属在高温下氧化形成的物质(Eu/SWNH-ox)的甲烷吸附密度的测定结果。另外，作为比较还测定作为甲烷吸附材料的A5(活性炭纤维)、A10(活性炭纤维)、A20(活性炭纤维)、AX21(高比表面积活性炭)和MCMB(活化中位碳(メソカ一ボン)微珠)的甲烷吸附密度。
从图3可以知道吸附到担载了镧族金属的SWNH中的甲烷吸附密度比其它碳材料的甲烷吸附密度更大。
<实施例2>
接着，将用激光烧蚀法制造的单层碳纳米突(SWNH)在氧气流、693K下氧化后，悬浮于乙醇中，然后，加入一定量的硝酸镧族元素的乙醇溶液，进行5分钟超声波处理后，蒸发干燥。使用的镧族元素是Eu，担载量是每1g的SWNH为0.1mmol。为了比较，还测定将SWNH在氧气流、693K下氧化的物质的甲烷吸附密度。其结果如表2和图4所示。
表2
| 样品 | 表面积(m<sup>2</sup>g<sup>-1</sup>) | 细孔容量(mLg<sup>-1</sup>) |
| SWNH-ox | 1010 | 0.47 |
| Eu/SWNH-ox | 780 | 0.33 |
在这种情况下，如表2所示，由于担载了Eu细孔容量有一定的减少，但是从图4可以知道甲烷吸附密度增大。
另外，如表2表明的那样，加热、氧化后的SWNH的细孔容量比表1的未加热、氧化的SWNH的细孔容量更大。
<实施例3>
将用激光烧蚀法制造的SWNH悬浮于乙醇中，加入一定量的硝酸镧族元素的乙醇溶液，进行5分钟超声波处理后，蒸发干燥。之后，将该样品在颗粒成形器中颗粒化。使用的镧族元素为Eu，担载量是每1g的SWNH为0.1mmol。测定它们的甲烷吸附量的结果如图5所示。另外，为了比较，将用激光烧蚀法制造的SWNH悬浮于乙醇中，用颗粒形成器颗粒化，制备样品。从图5可知，在该情况下，担载了Eu的SWNH颗粒的甲烷吸附量与通常的SWNH颗粒的情况相比，增加到约1.5倍。
如以上的详细说明，根据本申请的发明可以提供甲烷吸附量多，作为甲烷吸附材料有效的单层碳纳米突吸附材料及其制造方法。
Claims (4)
1.单层碳纳米突吸附材料的制造方法，其特征在于：将单层碳纳米突悬浮于乙醇中，然后加入一定量的硝酸镧、硝酸铕、硝酸铒以及硝酸镥中的任一种的乙醇溶液，再进行超声波处理后，蒸发干燥，将镧、铕、铒以及镥中的任一种担载在单层碳纳米突上。
2.根据权利要求1所记载的单层碳纳米突吸附材料的制造方法，其特征在于：制造具有甲烷吸附性的单层碳纳米突吸附材料。
3.根据权利要求1记载的单层碳纳米突吸附材料的制造方法，其特征在于：相对于每1g单层碳纳米突，镧、铕、铒以及镥中的任一种担载在单层碳纳米突上的担载量为大于等于0.01mmol、小于等于5mmol。
4.根据权利要求1记载的单层碳纳米突吸附材料的制造方法，其特征在于：在将单层碳纳米突悬浮于乙醇中之前，进行加热，在氧气流下进行氧化。
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| JP2003174016A JP4394383B2 (ja) | 2003-06-18 | 2003-06-18 | 単層カーボンナノホーン吸着材およびその製造方法 |
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| JP4723829B2 (ja) * | 2004-08-13 | 2011-07-13 | 独立行政法人科学技術振興機構 | 貴金属担持カーボンナノホーンの製造方法 |
| JP5013722B2 (ja) * | 2005-03-10 | 2012-08-29 | 独立行政法人科学技術振興機構 | ナノ金属微粒子／炭素ナノ繊維構造体の製造方法 |
| US20090196993A1 (en) | 2006-01-31 | 2009-08-06 | Sumio Iijima | Carbon Nanohorn Carried Material And Process For Producing Carbon Nanotube |
| JP5305347B2 (ja) * | 2009-02-27 | 2013-10-02 | 独立行政法人産業技術総合研究所 | 分岐型単層カーボンナノホーンとその分散液 |
| JP6068334B2 (ja) * | 2011-04-15 | 2017-01-25 | 株式会社環境・エネルギーナノ技術研究所 | カーボンナノ材料製造装置及びその利用 |
| CN105431379A (zh) * | 2013-08-02 | 2016-03-23 | 国立研究开发法人产业技术综合研究所 | 含有光响应性分散剂的含有分散剂的碳材料膜、使用该含有分散剂的碳材料膜的碳材料膜的制造方法 |
| US10813257B2 (en) * | 2016-09-05 | 2020-10-20 | Nec Corporation | Electromagnetic wave absorbing material |
| CN109966533A (zh) * | 2019-05-23 | 2019-07-05 | 李学书 | 一种利用碳纳米角制成的除臭剂及用途 |
| CN118079863B (zh) * | 2024-04-29 | 2024-06-28 | 四川大学 | 生物质衍生功能化多孔碳球固相吸附剂及其制备方法与应用 |
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| CN1805785A (zh) | 2006-07-19 |
| WO2004112955A1 (ja) | 2004-12-29 |
| EP1637223A4 (en) | 2009-01-07 |
| EP1637223A1 (en) | 2006-03-22 |
| US8007908B2 (en) | 2011-08-30 |
| US20060165992A1 (en) | 2006-07-27 |
| JP2005007281A (ja) | 2005-01-13 |
| JP4394383B2 (ja) | 2010-01-06 |
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