Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
Australian Journal of Chemistry

Australian Journal of Chemistry

Volume 65 Number 6 2012

RESEARCH FRONT: Artificial Photosynthesis: Energy, Nanochemistry, and Governance

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This introduction sets the papers collected for this special edition (that arose from the 2011 Lord Howe Island conference on Global Artificial Photosynthesis) in the context of the scientific and governance challenges for a Global Solar Fuels project. This special edition represents the first dedicated to such a theme and its significance is highlighted by the fact that 2012 is the United Nations’ Year of Sustainable Energy for All.

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Our present energy system stands on black roots; one decade into the new century fossil fuel sources are still more than 80 % of our primary energy. This paper discusses why we need to develop means to produce truly sustainable fuels, and proposes solar energy as the major renewable energy source to feed from.

CH12048Towards Hydrogen Energy: Progress on Catalysts for Water Splitting

Gerhard F. Swiegers, Douglas R. MacFarlane, David L. Officer, Amy Ballantyne, Danijel Boskovic, Jun Chen, G. Charles Dismukes, Graeme P. Gardner, Rosalie K. Hocking, Paul F. Smith, Leone Spiccia, Pawel Wagner, Gordon G. Wallace, Bjorn Winther-Jensen and Orawan Winther-Jensen
pp. 577-582
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This article reviews some of the recent work in the field of water oxidation and reduction catalysts by fellows and associates of the Australian Research Council’s Centre of Excellence for Electromaterials Science (ACES) at Monash University and the University of Wollongong, as well as their collaborators. This work is focussed on the development of a hydrogen-based energy technology. Topics discussed include: (1) the role and apparent relevance of the cubane 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.

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In natural light-harvesting systems, pigment-protein complexes (PPC) convert sunlight to chemical energy with near unity quantum efficiency. Studies using two-dimensional electronic spectroscopy (2DES) provide an incisive tool to probe the electronic, energetic, and spatial landscapes that enable the efficiency observed in photosynthetic light-harvesting. We review design principles of PPCs learned from the information contained within 2D spectra.

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The Mn4/Ca centre in Photosystem II is the most effective anodic water oxidizing catalyst known and operates close to the thermodynamic limit. This performance derives from redox properties of Mn in the oxidation states II–IV, which are uniquely ‘tuned’ to allow function with minimum overvoltage. Possible strategies to exploit this for efficient, biomimetic electrolytic H2 generation are discussed.

CH12016Preparation and Characterization of Catalysts for Clean Energy: A Challenge for X-rays and Electrons

Rosalie K. Hocking, Shery L. Y. Chang, Douglas R. MacFarlane and Leone Spiccia
pp. 608-614
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Key to elucidating the origin of catalytic activity and improving catalyst design is determining molecular-level structure, in both the ‘resting state’ and in the functioning ‘active state’ of the catalysts. Herein, we explore some of the analytical challenges important for designing and studying new catalytic materials for making and using hydrogen.

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Despite their importance in energy and chemical technologies, heterogeneous catalysts are often viewed as a ‘black box’, with their design bordering on alchemy. Advanced in situ X-ray spectroscopies are now enabling scientists to peer inside these functional nanomaterials and understand the inner workings of catalysts in action.

CH12024 On the Stability of Water Oxidation Catalysts: Challenges and Prospects

Alex Izgorodin, Orawan Winther-Jensen and Douglas R. MacFarlane
pp. 638-642
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Future requirements for water splitting technologies need highly efficient water oxidation catalysts that are sufficiently stable for operation over many years. In this paper, we discuss some of the chemical and thermodynamic challenges confronting this goal, as well as some of the strategies that are available to overcome them.

CH12096Perspectives for Photobiology in Molecular Solar Fuels

Kastoori Hingorani and Warwick Hillier
pp. 643-651
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Solar fuels are initiatives to harness sunlight and to generate storable fuels. Microbes can be genetically reprogrammed to produce algal fuels in the form of hydrocarbons and biodiesel. Artificial photosynthesis using proteins can also be produced. The goal with these systems is to use renewable solar energy and to catalyse energy conversion into a chemical bond. The paper outlines options and possible outcomes with solar energy conversion using photobiology.

CH11452Engineering Enzymes for Energy Production

David L. Ollis, Jian-Wei Liu and Bradley J. Stevenson
pp. 652-655
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Enzymes allow efficient conversion of biomass into useful chemical energy; however, they are seldom optimized for reaction conditions in biotechnology. Directed molecular evolution can be used to generate enzymes suited for new environments. As an example, we illustrate how yeast pyruvate decarboxylase 1 has been enhanced for in vitro fermentative glycolysis.

CH11437The Challenge of Storage in the Hydrogen Energy Cycle: Nanostructured Hydrides as a Potential Solution

James M. Hanlon, Hazel Reardon, Nuria Tapia-Ruiz and Duncan H. Gregory
pp. 656-671
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Nanochemical design methods offer routes to overcome the thermodynamic and kinetic hurdles associated with solid state storage in hydrides. In this review we discuss strategies of nanosizing, nanoconfinement, morphological/dimensional control, and application of nanoadditives on the hydrogen storage performance of metal hydrides and the potential role of such materials in a sustainable hydrogen cycle.

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A new radical of 2-(2-quinoxalinyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide was first designed and synthesised to afford four coordination sites to construct CuII and MnII complexes with more complicated structures and magnetic properties.

CH12168Novel Phosphopeptides as Surface-Active Agents in Iron Nanoparticle Synthesis

Raoul Peltier, Wai Ruu Siah, Grant V. M. Williams, Margaret A. Brimble, Richard D. Tilley and David E. Williams
pp. 680-685
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Wet chemical techniques are attractive methods for the preparation of metal nanoparticles. Here, we report the dramatic effect of rationally-designed phosphopeptides on the size, shape and magnetic properties of iron-iron oxide core-shell nanoparticles prepared in a one-pot synthesis by sodium borohydride reduction of an iron salt. These phosphopeptides are effective at small ratios of peptide to metal, in contrast to the behaviour of conventional surfactants, which must be added at high concentration to control the particle growth.

CH12039Bisiminopropadienes R-N=C=C=C=N-R from Pyridopyrimidines

Heidi Gade Andersen, David Kvaskoff and Curt Wentrup
pp. 686-689
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Chlorination of N,N′-di(2-pyridyl)malonamides affords 4-pyridylimino-4H-pyrido[1,2-a]pyrimidines 17. Flash vacuum thermolysis of 17a causes ring opening to a valence-tautomeric ketenimine, elimination of HCl, and formation of the bis(4-methyl-2-pyridylimino)propadiene, R-N=C=C=C= N-R 20a.

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Professor Kenneth Seddon OBE, one of AJC’s longest-standing Editors, sadly passed away on 21 January from prostate cancer. Ken was one of the world's best ionic liquids experts. His consistent unwavering support, loyalty and advocacy for AJC over the last 10 years will be sorely missed.