Gyroid镍纳米结构的嵌段共聚物超分子
Summary
本文介绍了有序的镍nanofoams 通过电镀金属沉积制备从上自组装嵌段共聚物为基础获得的超分子纳米多孔模板。
Abstract
纳米多孔金属泡沫体具有以下特性的独特组合， – 它们的催化活性，热和电传导性，而且，具有高孔隙率，高的表面与体积之和的强度 – 重量比。不幸的是，用于制备金属纳米结构的常见的方法使材料具有高度无序的结构，它可能对它们的机械性能有不利影响。嵌段共聚物具有的能力，以自组装成有序的纳米结构，并且可以作为用于良好有序金属nanofoams制备模板被应用。这里我们描述的嵌段共聚物为基础的超分子复合物的应用-聚苯乙烯- 嵌段 -聚（4 -乙烯基吡啶）（十五烷基）共聚物PS-b-P4VP（PDP） -作为前体为良序镍nanofoam。超分子复合物表现出类似传统嵌段共聚物的相行为，可以自组装成的双连续gyroid形态机智放置在P4VP（PDP）矩阵H两个PS网络。 PDP可以被溶解在乙醇中，导致可与金属回填多孔结构的形成。利用无电解镀法，镀镍可被插入到模板的通道。最后，将剩余的聚合物可通过从产生纳米多孔泡沫镍与逆gyroid形态学的聚合物/无机纳米杂化物的热解被除去。
Introduction
有可用于金属nanofoams准备几种方法：去合金1-3，溶胶-凝胶方法4,5，nanosmelting 6,7和燃烧合成8。在脱合金过程中，起始材料通常是二元合金，例如，银和金的合金。越少的贵金属银，在这种情况下，可通过化学或电化学产生了无序多孔金泡沫与纳米韧带除去。在燃烧合成，金属是一个充满活力的前体，它在分解过程中释放出能量和驱动器的金属nanofoam 8形成的混合。研究的金属泡沫材料的机械性能表明，在无序结构的应力不能被有效地从韧带纳米发送到整体宏观9-11，因此良好有序金属nanofoams预期相比，具有优越的机械性能无序的。
这里所表示的想法是使用嵌段共聚物自组装成有序的纳米结构前体对金属nanofoams。取决于嵌段共聚物中，单体单元的总数，并经化学连接块之间的斥力的范围的组成，各种形态出现，例如：球形，圆柱形，薄片状，双gyroid，六角形层状穿孔，而其他12-14 。此外，聚合物嵌段可以选择性地降解，导致纳米多孔材料15。最常用的方法包括：臭氧分解16-18，UV照射19，反应离子蚀刻20-22和23-26的溶解。所产生的多孔结构可被回填与各种无机材料。金属氧化物（ 如 SiO 2的，TiO 2的）通常是通过溶胶-凝胶法引入到模板的通道27-29。萨尔瓦多ectrochemical和电解电镀，通常用于沉积金属之中或之上的模板30-33。最后，将剩余的聚合物可以从通过热解2，溶解34,35，紫外线劣化28,29 等的聚合物/无机纳米杂化物去除
在我们的方法中，我们从聚苯乙烯- 嵌段 -聚（4 -乙烯基吡啶）的超分子复合物（PS-B-P4VP）嵌段共聚物和两亲十五烷基苯酚（PDP）的分子开始。这是复杂的PDP和吡啶环（ 图1a）之间的氢键的结果。起始嵌段共聚物的组合物和加入的PDP的量被选择在这样一种方式，所得到的体系自组装在双连续双gyroid形态与PS网络和一个P4VP（PDP）的基体（ 图1b）。 PDP分子变成选择性地溶解于乙醇和P4VP链崩溃到PS网络（图1c）。接着，用无电解电镀法，镍被沉积到模板（ 图1d）的孔中。 通过热分解除去残留的聚合物后，一个有序gyroid镍nanofoam得到（ 图1e）。
Protocol
1，准备和PS-B-P4VP的表征（PDP）配合双Gyroid形态称出聚苯乙烯- 嵌段 -聚（4 -乙烯基吡啶）（PS-β-P4VP）和十五烷基苯酚（PDP中，M R =304.51克/摩尔）。为了获得gyroid形态，（根据线性AB二嵌段共聚物的相图P4VP（PDP）的嵌段的重量分数（F P4VP（PDP））应为约 0.6），小心地选择PDP的量应。通常，0.15-0.2克共聚物PS-b-P4VP的导致共聚物PS-b-P4VP…
Representative Results
。超分子复合物的形态共聚物PS-b-P4VP（PDP）x由TEM和SAXS 图2a检查和2b显示的代表超分子配合物的典型gyroid模式：双波和已知代表货车轮图案通过（211）突起和（111）面的gyroid单元电池分别。 PS块域显得明亮而P4VP（PDP）×块域出现暗由于碘染色。 图2c代表了不同的gyroid样品，其中的周期性下降时用2。SAXS峰的一个因素的双波模式位置：√6Q *√8Q *√14Q *√22…
Discussion
超分子复合物的前体秩序井然金属nanofoams成功应用。在该方法中，关键的步骤是获得合适的模板， 即与gyroid形态的模板。在嵌段共聚物的相图的gyroid区域是非常小的，这是相当困难的目标。这意味着，如果常规的嵌段共聚物被用作起始原料时，相当精细的合成必须被重复，直到所希望的组合物，其引起的gyroid形态，就达到了。在共聚物PS-b-P4VP（PDP）的配合物不同的组合物，并且因此…
Disclosures
The authors have nothing to disclose.
Acknowledgements
我们承认财务支持格罗宁根大学的泽尼克研究所的高级材料。
Materials
| REAGENTS: | |||
| PS-b-P4VP, CAS: 26222-40-2 | Polymer Source Inc. | P9009-S4VP P136-S4VP P5462-S4VP P3912-S4VP |
additional information are provided in a separate table |
| PDP | Aldrich | P4402-100G-A | recrystallized twice from petroleum ether |
| SnCl2 | Acros Organics | 196981000 | |
| PdCl2 | Aldrich | 76050 | |
| NiSO4 x H2O | Sigma-Aldrich | 227676 | |
| lactic acid | Aldrich | W261106 | |
| citric acid trisodium salt | Sigma-Aldrich | C3674 | |
| borane dimethyl amine complex | Aldrich | 180238 | |
| PS-b-P4VP catalogue number | Mn (PS), g/mol | Mn(P4VP), g/mol | PDI |
| P9009-S4VP | 24000 | 9500 | 1.1 |
| P136-S4VP | 31900 | 13200 | 1.08 |
| P5462-S4VP | 37500 | 16000 | 1.3 |
| P3912-S4VP | 41500 | 17500 | 1.07 |
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Cite This Article
Vukovic, I., Punzhin, S., Voet, V. S. D., Vukovic, Z., de Hosson, J. T. M., ten Brinke, G., Loos, K. Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules. J. Vis. Exp. (86), e50673, doi:10.3791/50673 (2014).