Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

Synthesis of porous graphene/TiO2 by use of recycled graphite

Graphene-based nanomaterials are a kind of new technological materials with high interest for physicists, chemists and materials scientists. Graphene is a two-dimensional (2-D) sheet of carbon atoms in a hexagonal configuration with atoms bonded by sp2 bonds. These bonds and this electron configuration provides the extraordinary properties of graphene, such as very large surface area, a tunable band gap, high mechanical strength and high elasticity and thermal conductivity [1]. Graphene has also been investigated for preparation of composites with various semiconductors like TiO2, ZnO, CdS aiming at enhanced photocatalytic activity for their use for photochemical reaction as water splitting or CO2 to methanol conversion [2-3]. In this communication, the synthesis of porous graphene@TiO2 obtained from a powder graphite recycled, supplied by ECOPIBA, is presented. This graphite was exfoliated, using a nonionic surfactant (Triton X-100) and sonication. Titanium(IV) isopropoxide was used as TiO2 source. After removing the surfactant with a solution HCl/n-propanol, a porous solid is obtained with a specific area of 358 m2g-1. The solid was characterized by XRD, FTIR, XPS, EDX and TEM. Figure 1 shows the graphene 2D layer bonded with nanoparticles of TiO2. When a water suspension of this material is exposed with UV-vis radiation, water splitting reaction is carried out and H2/O2 bubbles are observed (Figure 2)