Towards hydrogen energy: progress on catalysts for water splitting

This article reviews some of the recent work by fellows and associates of the Australian Research Council Centre of Excellence for Electromaterials Science (ACES) at Monash University and the University of Wollongong, as well as their collaborators, in the field of water oxidation and reduction catalysts. This work is focussed on the production of hydrogen for a hydrogen-based energy technology. Topics include: (1) the role and apparent relevance of the cubane-like structure of the Photosystem II Water Oxidation Complex (PSII-WOC) in non-biological homogeneous and heterogeneous water oxidation catalysts, (2) light-activated conducting polymer catalysts for both water oxidation and reduction, and (3) porphyrin-based light harvesters and catalysts

Using Polarized Spectroscopy to Investigate Order in Thin-Films of Ionic Self-Assembled Materials Based on Azo-Dyes

Three series of ionic self-assembled materials based on anionic azo-dyes and cationic benzalkonium surfactants were synthesized and thin films were prepared by spin-casting. These thin films appear isotropic when investigated with polarized optical microscopy, although they are highly anisotropic. Here, three series of homologous materials were studied to rationalize this observation. Investigating thin films of ordered molecular materials relies to a large extent on advanced experimental methods and large research infrastructure. A statement that in particular is true for thin films with nanoscopic order, where X-ray reflectometry, X-ray and neutron scattering, electron microscopy and atom force microscopy (AFM) has to be used to elucidate film morphology and the underlying molecular structure. Here, the thin films were investigated using AFM, optical microscopy and polarized absorption spectroscopy. It was shown that by using numerical method for treating the polarized absorption spectroscopy data, the molecular structure can be elucidated. Further, it was shown that polarized optical spectroscopy is a general tool that allows determination of the molecular order in thin films. Finally, it was found that full control of thermal history and rigorous control of the ionic self-assembly conditions are required to reproducibly make these materials of high nanoscopic order. Similarly, the conditions for spin-casting are shown to be determining for the overall thin film morphology, while molecular order is maintained

New one-pot poly(3,4-ethylenedioxythiophene): poly(tetrahydrofuran) memory material for facile fabrication of memory organic electrochemical transistors

The discovery of a new poly(3,4-ethylenedioxythiophene) (PEDOT) composite with unique memory characteristics has led to the demonstration of durable Organic ElectroChemical Transistors (OECT) based memory devices. The composites of PEDOT with polytetrahydrofuran undergo a structural collapse during electrochemical reduction that requires approximately 800 mV overpotential to re-open and is thus hindering the re-oxidation of the composite. This effect causes the composite at intermediate potentials to be able to have two different oxidation states and thereby resistances, depending on the “on” or “off” switching potential applied prior to the intermediate potential. Notably, this hysteresis is lasting over time and no drift has been observed. Impedance spectroscopy, in-situ UV-Vis spectroscopy, conductivity measurement, in-situ electrochemical quartz crystal microbalance, and differential scanning calorimetry were used to confirm and explain the switching memory phenomena. The OECT platform was used to validate the PEDOT:PTHF as a one-pot memory source-drain material where a threefold increase in drain current was observed between “off” and “on” mode of the transistor after modulation of the Ag/AgCl gate