EPSRC DTP Studentship - Nitrogen-rich compounds as energetic materials and precursors for novel nitrides

Details

Nitrides (covalent chemical compounds solely consisting of nitrogen and one other chemical element) have great potential for applications due to their highly interesting semiconducting, photocatalytic, optical, and mechanical properties, with a recent industry-led boom in search for efficient synthetic methods and the associated need for a full understanding of their properties. The research project focuses on nitrogen-rich heterocycles (e.g., poly(tetrazolyl)triazines, 74% N) and nitrogen-rich coordination compounds of light p-block elements as highly promising precursors for nitrides such as CxNy, GexNy, BxNy, and developing simple chemical synthetic routes to such nitrides. Of particular note are the well-established silicon nitride (Si3N4) and the hypothetical carbon nitride (C3N4), the latter being suspected to exceed the hardness of the hardest known material (diamond). An improved understanding of nitride-forming reaction pathways, and full characterisation of precursors and products (electronic and structural on molecular and material levels) is also urgently required. Conventional methods often use mixtures of volatile starting material which are subjected to a chemical vapour deposition processes that require high or very high temperatures, thus preventing the formation of yet unknown, thermally less stable, nitrides which is the challenge our research seeks to address. Novel materials such as these are essential for future development in the chemical foundations of materials science.

The PhD project work will concentrate on systematically establishing the synthesis of novel azides and tetrazoles of boron, carbon, silicon and germanium, as chemical precursors in nitride forming reactions, followed by their characterisation according to the standards of the discipline of inorganic coordination chemistry. Well-characterised compounds will be subjected to quantitative thermal decomposition studies involving a variety of reaction monitoring techniques and ab initio quantum chemical calculations. In a collaborative effort with Joe Harrity and Grant Hill, both at Sheffield, the researcher will determine the mechanism for thermally induced decomposition and ascertain prospects of nitride formation as well as draw structure – property relationships. Candidate that have passed this stage will then be used to generate novel nitrides following the low-temperature method.

The successful applicant will join an experienced and diverse team based at the Department of Chemistry as part of a Russel Group university to carry out primarily chemical experimental and computational work with an opportunity to adjust focus at later project stages. Training will be given for a multitude of methods (such as advanced synthetic chemistry of air sensitive compounds, single crystal and powder X-ray crystallography, mass spectrometry, evolved gas analysis, vibrational and resonance spectroscopies, time-resolved IR spectroscopy, computational chemistry, multinuclear NMR spectroscopy). The researcher will furthermore benefit from the departmental doctoral training programme and the usual activities of conference presentations and publication efforts. Ample need and opportunity is programmed into the research to engage with well-established experts in the field in computational chemistry (Dr Grant Hill), materials characterisation (Professor Colin Pulham) and organic synthesis of N-heterocycles (Professor Joe Harrity).

For more information, please contact Dr Portius ( p . portius @ sheffield . ac . uk ) and see https://www.sheffield.ac.uk/chemistry/people/academic/peter-portius

Project ID: CHM-09-Portius

To apply for a PhD place, you will need to complete an online application form. Please follow this link for the form.

Interested candidates are strongly encouraged to contact the project supervisors to discuss your interest in and suitability for the project prior to submitting your application. 

Please refer to the EPSRC DTP webpage for detailed information about the EPSRC DTP and how to apply.