PhD Studentship in Homogeneous Catalysis
Catalytic CO2 Hydrogenation to CH3OH and HCO2CH3: New ‘Frustrated Lewis Pairs’ for Homogeneous CO2-to-Fuel Conversions
Applications are sought for a fully funded 3.5 year studentship in homogeneous catalysis and small molecule activation. The successful candidate will be supervised by Dr Andrew Ashley at the new state-of-the-art Molecular Sciences Research Hub, Imperial College London, starting October 2020.
Project: This research project targets the use of activated H2 using ‘frustrated Lewis pairs’ to deliver reducing equivalents (H·, H+, H–) to CO2. This will be mediated by low-coordinate hydride species and proceed via unusual oxidative addition/reductive elimination cycles on a main-group element, to catalytically effect the stepwise catalytic reduction of CO2 to CH3OH.
One of the grand challenges facing chemists is to find a method of catalytically, and selectively, hydrogenating CO2 to liquid fuels; if the H2 is renewably sourced this is a route to carbon-neutral fuels. The activation of both H2 and CO2 can be achieved using abundant main-group elements, which is encompassed within the rapidly advancing field of ‘frustrated Lewis pair’ (FLP) chemistry. Examples of FLP hydrogenations catalysed by p-block elements exist for a wide variety of organic (e.g. carbonyls, imines) and inorganic substrates, and we have previously reported a system based on B(C6F5)3 to stoichiometrically transform CO2/H2 mixtures into CH3OH. Recently we have been investigating Sn(II) and Sn(IV) Lewis acid components in FLPs; the Sn centre is soft, which leads to unique reactivity. Excitingly, these activate H2 (sometimes via oxidative addition) and catalytically reduce C=O bonds, yet we have not applied this methodology to CO2. This project will involve the synthesis of new, bulky Sn hydrides to investigate the kinetic aspects of their reactivity with H2/CO2 mixtures, using isotopic labelling and React-IR techniques. This approach will enable structure-function relationships to be derived and hence rational optimisation of the catalyst system towards an industrially competitive protocol to produce CH3OH and other commercially important oxygenates (e.g. CH3OCH3).
Eligibility and Funding: The position would suit an ambitious and highly motivated researcher with interests in organometallic chemistry and catalysis. A strong background in air-sensitive synthetic chemistry is desirable, with relevant previous research experience in academic laboratories essential. Funding is available to UK/EU students and will cover tuition fees and provide a tax-free stipend, including a London allowance. Applicants should hold (or expect to be awarded) a Class 1 Masters degree (MSci, MChem) in Chemistry. The chosen candidate will subsequently be entered for a highly prestigious Imperial College President's PhD Scholarship which offers the highest achievers in their undergraduate cohort (typically top 5-10%) an outstanding opportunity to receive a higher stipend (> £20,000 p.a.) for 3.5 years, and to access a structured programme of career development. For further information please click here.
How to Apply: Interested candidates are encouraged to make informal contact ASAP with Dr Ashley by email (email@example.com), enclosing a CV. Formal applications should be made through the Imperial College online application process, which can be accessed here. Please make reference to the above project title in the Proposed Research Topic field. Short-listed candidates will be required to attend an interview in person at Imperial College London, which will be held in mid-January 2020.
Research website: http://www.ashleyresearchgroup.org.uk/
For further details, see HERE