We propose to investigate the catalytic role of Fe-Ni sulfide cubane clusters and minerals in reactions involving organic compounds. Many of the key steps in the prebiotic syntheses of biological molecules that led to the emergence of life on Earth may have involved cubane FeS clusters (Russell and Hall, 1997, 2005). These clusters are present at active sites in compounds essential to modern life (e.g. hydrogenase, CODH and ACS enzymes) leading to the theory that the highly reactive surfaces of minerals like mackinawite and greigite, which should have been common in hydrothermal mounds at the Hadean ocean floor, acted as “building blocks” during fabrication of the prebiotic compounds. Technological applications of this research include identification of the catalytic role of Fe-Ni sulfide cubane clusters in (i) isolation of H2 for a future hydrogen-based energy cycle, (ii) synthesis of large organic molecules for the pharmaceutical and chemical industries, and (iii) environmental monitoring and control. We will compare the reactivity of both clusters and mineral surfaces using combined experimental and computational methods. (Fe,Ni)S cubane clusters will be synthesized and studied in detail, together with natural minerals, using structural (XRD), microscopical (;FTIR) and spectroscopic (EXAFS, XANES, ESR, XPS, Mossbauer) techniques. Computer modelling (molecular dynamics and density functional theory) will be used to determine the geometry and internal structure of synthetic clusters and natural minerals, and to investigate reactions at their surfaces with H2, CO and amino acids. This information will define the energetically favoured structures whose formation is the initial step in H2 oxidation and CO2 reduction, reactions that will be studied ekectrochemically with ultramicroelectrodes or graphite or platinum electrodes coated with an (Fe,Ni)S thin film. Although previous attempts to investigate the reactivity of the FeS site have only been partially successful, we expect the trans-national cutting-edge expertise of the 7 groups involved in the project to make significant advances in the mineral catalysis of the two chosen reactions that are so critical to the emergence of life on Earth.
Professor Laurent Charlet (Project Leader)
Géochimie de l‘Environnement, Laboratoire de Geophysique Interne et Tetonophysique OSUG, IRIGM, Université Joseph Fourier, Grenoble, France
Professor Nicholas T. Arndt
Université Joseph Fourier – Grenoble 1, Saint Martin d’Hères, France
Dr. Juan Fontecilla-Camps; Dr. Anne Volbeda
Institut de Biologie Structurale “Jean-Pierre Ebel”, Grenoble, France Dr. Sylvain Franger; Professor Jean-Jacques GirerdUniversité Paris-Sud 11, Orsay, France
Dr. Manuel Munoz; Dr. Michael J. Russell; Dr. Olivier Vidal
Université Joseph Fourier – Grenoble 1, St Martin d’Hères, France
Dr. Ricardo Amils Pibernat
Universidad Autónoma de Madrid, Madrid, Spain
Dr. Ian Butler; Professor David Terence Rickard
Cardiff University, Cardiff, United Kingdom
Dr. Nora Henriette de Leeuw
University College London, London, United Kingdom
Professor William Martin
Heinrich-Heine Universität, Düsseldorf, Germany
Dr. Mariëtte Wolthers; Dr. Paul Mason; Professor Christopher James Spiers; Professor Philippe Van Cappellen
Universiteit Utrecht, Utrecht, The Netherlands
