Hydrogen Chemistry at Ferracyclic Centres Related to the Mono – Iron Hydrogenase
Biochemistry, Electrochemistry, Inorganic Chemistry, Physical Chemistry, Synthetic Chemistry
Deadline:Â 1st April 2013. This studentship is available for a 1st October 2013 start.Â
Supervisory Team: Primary: Professor Christopher Pickett (School of Chemistry)
In catalysis and electrocatalysis related to dihydrogen generation and utilisation there are economic and sustainability drivers for the replacement of precious metals by (electro)catalysts based upon earth abundant metals. For example, platinum is the electrocatalyst of choice in low temperature fuel/producer cells but the supply side is arguably unsustainable if there is a significant growth in a hydrogen based economy. Scarce metals such as rhodium, ruthenium, iridium and platinum metals are widely used in industrial hydrogenation and hydrosilyation chemistry at scales where catalyst attrition is a considerable cost. Replacement by cheaper metal catalysts is attracting considerable attention. Recently high activity of Fe systems that can replace Rh in hydrosilyation catalysis has been reported and âruthenium-liteâ chemistry for asymmetric hydrogenation has been described.Â In the area of hydrogen generation, there is much current activity in exploring electrocatalytic chemistry related to the active sites of the hydrogenases and also of systems which, though not directly bioinorganic, have similar operational features. Such catalytic chemistry is also playing a role in the construction of photoelectrocatalytic and nanoparticle semi-conductor assemblies for solar fuel generation.
This project is specifically concerned with the emerging chemistry of the mono-iron hydrogenase, Hmd. The natural system cleaves dihydrogen heterolytically, releasing a proton and placing a hydride onto an organic substrate. We have recently synthesised close structural analogues of the active site which possess the stable five membered ferracyclic ring found in the natural system. The plan is to activate these molecules for catalysis by introducing an anchored hemi-labile basic group at the iron centre – tethered groups which are capable both of unmasking a dihydrogen binding site and promoting its heterolytic cleavage. A collaboration with Professor Jin at the Laboratory for Advanced Materials, Fudan will provide access to a promising class of hemi-labile ligands based on di-functionalised carboranes possessing a thiolate anchoring group and a basic P=S hemi-labile moiety. New ferracyclic materials will be characterised by a range of methods, including X-ray crystallography. Catalytic reactivity in hydride transfer to organic substrates will be explored using a range of techniques including high pressure infrared and stopped flow FTIR kinetic measurements. In summary, the research student will receive training and gain experience in the design, synthesis and characterisation of novel materials and of using advanced techniques to study mechanistic aspects of their catalytic activity in a project involving international collaboration in an emerging area of hydrogenase chemistry, sustainability and energy transduction.
A first class UK honours degree, or the equivalent qualifications gained outside the UK, in Chemistry.
This project is specifically funded for international students only. This funding includes full tuition fees and an annual stipend of Â£13,726. Funding is available for 3 years. Home/EU students are still welcome to apply provided they are able to secure their own source of funding.
Making Your Application: Please apply via the Universityâs online application system. Â To discuss the application process or particular projects, please contact the:Â Admissions Office, email: [email protected] or telephone +44 (0)1603 591709.