Confined Molecular Clusters

Completed

Not Energy Related
Hydrogen and Fuel Cells(Fuel Cells)

Basic and strategic applied research

PHYSICAL SCIENCES AND MATHEMATICS (Chemistry)

Not Cross-cutting

Dr A Weller
Oxford Chemistry
University of Oxford

Standard

EPSRC

01 October 2010

30 September 2013

36 months

£1

No relevance to Underpinning Sectors

South East

Physical Sciences

Dr A Weller, Oxford Chemistry, University of Oxford

This collaborative project between experimental and theoretical chemists will deliver well-defined transition-metal complexes that bridge the gap between the molecular and nano-scale regimes of chemical structure. Such materials will have a major impact on fundamental and applied organometallic and nano-particle research and technologies - further establishing a new, intermediate, size-regime in chemical synthesis and reactivity.The chemistry and technological applications, of nanoparticles are well-established (e.g. catalysis / functional materials), and the synthesis of materials of defined-shape (e.g., sphere, rod, star), size (i.e. monodisperse) and function is now commonplace. However, significant questions still remain with regard to the nature of the metal surface, the interactions between this and incoming substrates and onward reactivity-modes of surface-bound species. By contrast Organometallic chemistry (e.g. of 1 to 6 metal atoms) has played a keystone role in catalysis, small molecule activation and the development of theories in structural and bonding. In no small way this is due to the ability to interrogate at the molecular level structure and reactivity (using, e.g., NMR, X-ray crystallography, ESI-MS, computation). This proposed ambitiously seeks to bridge the gap between molecular and nanoscale regimes.We suggest that novel materials that have metal counts of between 7 and 55 are accessible under suitable kinetic regimes of self-assembly, and that these structures (electronic and geometric) and reactivity of materials can be described and predicted by computational techniques. We describe these materials as confined molecular clusters (CMCs). These well-defined materials designed with a surface that is hydride shrouded phosphine will be prepared, stabilised by bulky phosphine groups. Kinetic control (e.g., temperature, pressure, hydrogenation kinetics, concentration) and judicious choice of starting reagents (same/mixed metal, phosphine cone angle) will allow for a wide-range of composition and structure. Computational techniques will be used and developed to allow for both use as a characterising tool (predict hydride locations, fluxionality, gross core structure, EPR and NMR parameters) and as a predictive tool (magic numbers, properties, chemical reactivity). These new materials would be particularly interesting in terms of true models for nanoparticles, and thus have immediate relevance to catalysis, fuel cells and electronic materials. Indeed as highlighted by the US DOE the priority areas in basic fuel cell technology are "nanoscale catalyst design, highly active cathodes for low temperature processes and theory, modelling and simulation"

21/09/11