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

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

Graphene/zinc nano-composites by electrochemical co-deposition

We describe for the first time the electrochemical co-deposition of composites based on a reactive base metal and graphene directly from a one-pot aqueous mixture containing graphene oxide and Zn2+. In order to overcome stability issues the Zn2+ concentration was kept below a critical threshold concentration, ensuring stable graphene oxide suspensions in the presence of cationic base metal precursors. This approach ensures the compatibility between the cationic base metal precursor and graphene oxide, which is more challenging compared to previously reported anionic noble metal complexes. Spectroscopic evidence suggests that the reason for destabilisation is zinc complexation involving the carboxylate groups of graphene oxide. The composition of the electrodeposited co-composites can be tuned by adjusting the concentration of the precursors in the starting mixture. The nano-composites show zinc particles (<3 nm) being uniformly dispersed amongst the graphene sheets. It is also demonstrated that the composites are electrochemically active and suitable for energy storage and energy conversion applications. However, a factor limiting the discharge efficiency is the reactivity of the base metal (low reduction potential and small particle size) which undergoes rapid oxidation when exposed to aqueous electrolytes

A solid-state pH sensor for nonaqueous media including ionic liquids

We describe a solid state electrode structure based on a biologically derived proton-active redox center, riboflavin (RFN). The redox reaction of RFN is a pH-dependent process that requires no water. The electrode was fabricated using our previously described \u27stuffing\u27 method to entrap RFN into vapor phase polymerized poly(3,4-ethylenedioxythiophene). The electrode is shown to be capable of measuring the proton activity in the form of an effective pH over a range of different water contents including nonaqueous systems and ionic liquids (ILs). This demonstrates that the entrapment of the redox center facilitates direct electron communication with the polymer. This work provides a miniaturizable system to determine pH (effective) in nonaqueous systems as well as in ionic liquids. The ability to measure pH (effective) is an important step toward the ability to customize ILs with suitable pH (effective) for catalytic reactions and biotechnology applications such as protein preservation

High rates of oxygen reduction over a vapor phase-polymerized PEDOT electrode

The air electrode, which reduces oxygen (O2), is a critical component in energy generation and storage applications such as fuel cells and metal/air batteries. The highest current densities are achieved with platinum (Pt), but in addition to its cost and scarcity, Pt particles in composite electrodes tend to be inactivated by contact with carbon monoxide (CO) or by agglomeration. We describe an air electrode based on a porous material coated with poly(3,4-ethylenedioxythiophene) (PEDOT), which acts as an O2 reduction catalyst. Continuous operation for 1500 hours was demonstrated without material degradation or deterioration in performance. O2 conversion rates were comparable with those of Pt-catalyzed electrodes of the same geometry, and the electrode was not sensitive to CO. Operation was demonstrated as an air electrode and as a dissolved O2 electrode in aqueous solution.<br /