Micellar formation by soft template electropolymerization in organic solvents

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.