About the Project
The challenge of providing sufficient clean energy to power the industrialised world is well established. Addressing this will require a multi-stranded approach, not only developing new ways of generating energy but also cutting our energy usage.
A key but often forgotten energy use is the fixation of nitrogen: this is the first stage of making fertilizer, on which our food production depends. The Harber process has been used for this for well over 100 years but is extremely energy-intensive. At the same time, microbes are able to fix nitrogen under benign conditions using enzymes based on iron and molybdenum centres. Doing the same using small molecules in the laboratory offers the potential to provide the vital nitrogen-based starting materials we need at reduced energy and financial cost. Developing effective and stable systems to do this is one of the key challenges in organometallic chemistry today.
In this PhD project, we will tackle this challenge using a combination of synthetic organometallic chemistry and specialised mechanistic techniques. The use of secondary interactions is now well-established in nitrogen fixation,i and this project will focus on developing new ligand architectures to create novel mononuclear iron systems which can activate dinitrogen at low overpotentials. A key starting point will be the combination of our existing expertise in iron chemistry,ii,iii in combination with advanced spectroscopiesiv to deepen our understanding of the reactivity of these systems.
The PhD project involves synthesis of mononuclear iron-dinitrogen complexes, their characterisation by X-ray crystallography and a range of spectroscopic techniques, and study of their reactivity using stopped-flow and electrochemical techniques. Thus, it will provide a very broad-based training in inorganic synthesis, molecular characterisation and physical measurement, in the excellent facilities of the interdisciplinary Energy Materials Laboratory.
The project may be available to start earlier than October 2018, but candidates should discuss this with the primary supervisor in the first instance.
For more information on the supervisor for this project, please go here: https://www.uea.ac.uk/chemistry/people/profile/joseph-wright
Type of programme: PhD
Start date: October 2018
Full-time
Funding Notes
This PhD project is offered on a self-funding basis. It is open to applicants with funding or those applying to funding sources. Details of tuition fees can be found at http://www.uea.ac.uk/study/postgraduate/research-degrees/fees-and-funding.
A bench fee is also payable on top of the tuition fee to cover specialist equipment or laboratory costs required for the research. The amount charged annually will vary considerably depending on the nature of the project and applicants should contact the primary supervisor for further information about the fee associated with the project.
Acceptable first degree: Chemistry, Biochemistry.
The standard minimum entry requirement is 2:1.
References
i) Creutz, S. E. & Peters, J. C. Exploring secondary-sphere interactions in FetextendashNxHy complexes relevant to N2 fixation, Chem. Sci., 2017, 8, 2321
ii) Danopoulos, A. A.; Wright, J. A. & Motherwell, W. B., Molecular N2 complexes of iron stabilised by N-heterocyclic 'pincer' dicarbene ligands, Chem. Commun., 2005, 41, 784.
iii) Turrell, P. J.; Wright, J. A.; Peck, J. N. T.; Oganesyan, V. S. & Pickett, C. J. The Third Hydrogenase: A Ferracyclic Carbamoyl with Close Structural Analogy to the Active Site of Hmd, Angew. Chem. Int. Ed., 2010, 49, 7508
iv) Jablonskytė, A.; Wright, J. A.; Fairhurst, S. A.; Webster, L. R. & Pickett, C. J. [FeFe] Hydrogenase: Protonation of {2Fe3S} Systems and Formation of Super-reduced Hydride States, Angew. Chem. Int. Ed., 2014, 53, 10143
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