Fradin Caroline, Orange François, Amigoni Sonia, Szczepanski Caroline R, Guittard Frédéric, Darmanin Thierry
Université Côte d'Azur, NICE Lab, 06100 Nice, France.
Université Côte d'Azur, Centre Commun de Microscopie Appliquée (CCMA), 06100 Nice, France.
J Colloid Interface Sci. 2021 May 15;590:260-267. doi: 10.1016/j.jcis.2021.01.038. Epub 2021 Jan 20.
The formation of porous nanostructures on surfaces and the control of their size and shape is fundamental for various applications. The creation of nanotubes is particularly difficult to implement without the aid of hard and rigid templates. Recently, methods that form nanotubular structures in a straightforward manner and without direct templating, e.g. soft templating, have been highly sought after. Here we propose the use of "soft templating" via self-assembly of conducting monomers during electropolymerization in organic solvents as a mean to form porous, nanotubular features.
Naphtho[2,3-b]thieno[3,4-e][1,4]dioxine (NaphDOT) is employed as monomer for electropolymerizations conducted in dichloromethane and chloroform containing varying amounts of water. SEM analyses of the resulting surfaces confirms the strong capacity of NaphDOT to form vertically aligned nanotubes. Polymerization solutions analyzed by DLS and TEM reveal the presence of micelles prior to electropolymerization, and the size of the micelles correlates with the inner diameter of the nanotubes formed.
We show that micelles in polymerization solutions are stabilized by both monomers and electrolytes. We propose a mechanism where reverse micelles are forming a soft-template responsible for the formation of porous nanostructures during electropolymerization in organic, non-polar solvents. In this mechanism, the monomer and electrolyte assume the role of surfactant in the reverse micelle system.
在表面形成多孔纳米结构并控制其尺寸和形状对于各种应用至关重要。在没有坚硬且刚性模板的帮助下，制备纳米管尤其困难。近来，以直接方式且无需直接模板（例如软模板）形成纳米管结构的方法备受追捧。在此，我们提出在有机溶剂中进行电聚合过程中，通过导电单体的自组装来使用“软模板”，以此形成多孔的纳米管特征。
萘并[2,3 - b]噻吩并[3,4 - e][1,4]二恶英（NaphDOT）被用作在含有不同水量的二氯甲烷和氯仿中进行电聚合的单体。对所得表面进行扫描电子显微镜（SEM）分析证实了NaphDOT形成垂直排列纳米管的强大能力。通过动态光散射（DLS）和透射电子显微镜（TEM）分析聚合溶液，发现在电聚合之前存在胶束，并且胶束的大小与所形成纳米管的内径相关。
我们表明聚合溶液中的胶束由单体和电解质共同稳定。我们提出了一种机制，即反胶束形成软模板，负责在有机非极性溶剂中的电聚合过程中形成多孔纳米结构。在这种机制中，单体和电解质在反胶束体系中充当表面活性剂的角色。
