Selective Fabrication of Poly(3,4‐ethylenedioxythiophene) Nanocapsules and Mesocellular Foams Using Surfactant‐Mediated Interfacial Polymerization

Abstract

Recently, there has been great interest in the fabrication and application of nanomaterials with diverse structures. Interfacial polymerization (IP) [1] has enabled the fabrication of specific architectures such as films, fibers, and membranes. [2] Recently, considerable effort has been devoted to the synthesis of conducting-polymer nanomaterials using IP. Most previous studies have focused on polypyrrole (PPy) or polyaniline (PANi) nanostructures. [3] In contrast, there is not much information available regarding the synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) nanomaterials in spite of their various applications, including use as polymer light-emitting diodes, transparent antistatic coatings, and sensors.[4]Furthermore, it is still extremely difficult to synthesize PEDOT nanocapsules and mesocellular foams by means of IP.[5] Therefore, a facile and reliable method needs to be developed to easily fabricate these PEDOT nanostructures.Here, we report a novel surfactant-mediated interfacial polymerization (SMIP) method to selectively fabricate PEDOT nanocapsules and mesocellular foams. This represents the first demonstration of the selective fabrication of conducting-polymer nanostructures by controlling the surfactant concentration in the IP process. Furthermore, the electrochemical performance of the PEDOT nanomaterials has been evaluated to investigate their capabilities as supercapacitors. An overall synthetic procedure for PEDOT nanocapsules and mesocellular foams is illustrated in Scheme 1. Cationic surfactants, such as octyltrimethylammonium bromide (OTAB, critical micelle concentration (CMC) = 0.22 M), decyltrimethylammonium bromide (DeTAB, CMC = 0.065 M), and dodecyltrimethylammonium bromide (DoTAB, CMC = 0.016 M), are used to control the morphology of the PEDOT nanomaterials. [6] A variable amount of surfactant is dissolved in distilled water for the formation of micelles. Subsequently, cerium ammonium nitrate (CAN, Ce(NH 4 ) 2 (NO 3 ) 6 ) is added to the micelle solution as a polymerization initiator; the CAN-micelle solution is designated solution A (Scheme 1a). The micelles are able to capture the redox initiator (CAN) due to electrostatic interactions between the cerium complex and the surfactant molecules, and this allows the initiator to exist at the micelle/water interface. [7] Separately, the EDOT monomer is dissolved in cyclohexane, and the monomer solution is called solution B (Scheme 1b). Solution A is then introduced dropwise into solution B, and the EDOT monomer comes into contact with CAN at the micelle interface.

Preparation of a hybrid core–shell structured BaTiO 3 @PEDOT nanocomposite and its applications in dielectric and electrode materials

“…However, for BaTiO 3 @PEDOT composites, a faint oxidation peak can be observed at 0.25 V, and the reverse reduction wave is visible at -0.25 V. These peaks may be due to the redox transition of PEDOT between a semiconducting state and a conducting state. Similar peaks were observed by Jang et al in their electrochemical study of PEDOT nanoparticles [35].…”

Versatile strategies for fabricating polymer nanomaterials with controlled size and morphology

“…The second case has been realized by using a wide variety of soft templates (e.g., surfactants, polyelectrolytes, and liquid crystals) [216][217][218][219][220][221][222] and hard templates (e.g., colloidal nanoparticles and porous materials). 223,224 It is usually difficult to create nanoporous polymer structures under polymerization or casting conditions due to thermodynamic instability, in contrast with the case of porous silica families such as MCM-41 and SBA-15.…”

“…A recent study demonstrated that the socalled "surfactant-mediated interfacial polymerization" was effective to selective fabrication of PEDOT nanostructures with nanometer-sized cavities. 219 At first stage, cationic ammonium surfactants with different alky chain lengths were used to form micelles in aqueous solution. The micelles were able to capture the redox initiator (CAN) due to electrostatic interactions between the cerium complex and the surfactant molecules, and the chemical polymerization of EDOT monomer proceeded at the micellar surface.…”

Reactive template method for the synthesis of Pd nanoparticles supported PoPd hollow spheres for electrochemical oxidation of ascorbic acid

“…Recently, PoPD hollow spheres decorated with Au and AgNs using monomer droplet method [10] have been reported. In this method, PoPD hollow spheres are synthesized in aqueous media, by means of the droplet template formed by the monomer itself without the aid of acidic reagent [11], surfactants [12] or hard templates [13]. These droplets (reactive template) formed by the monomer in aqueous solution are proposed to act as a template during the polymerization process [14].…”