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Polymerising, depolymerising and repurposing using iron catalysis

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  • Full or part time
    Dr Ruth Webster
  • Application Deadline
    No more applications being accepted
  • Competition Funded PhD Project (Students Worldwide)
    Competition Funded PhD Project (Students Worldwide)

Project Description

The Centre for Sustainable Chemical Technologies (CSCT) at the University of Bath has launched a joint PhD programme with Monash University, Australia.

This project is one of a number that are in competition for up to four funded studentships. More details are available here: http://www.csct.ac.uk/study-with-us/

Home institution: Bath University
Supervisor at Bath: Dr Ruth Webster (lead)
Supervisor at Monash: Sara Kyne

Overview

The synthesis and activation of Si-E bonds is increasing due to the importance of silicon chemistry, which has uses that span from materials chemistry (e.g. semiconductors, polymers, composite ceramics) to organosilicon compounds (e.g. protecting groups, coupling partners for cross-couplings). The depolymerisation and reuse of monomers from plastics is important, but is currently limited to hydrocarbon- or biorenewable-based polymers. Also of critical importance are polymers used in ceramics, coatings and lubricants, which are heteroatom rich and, at the end of their lifetime, could have a vast range of uses in modern chemical building block synthesis.
In this context, the dehydrocoupling synthesis and subsequent activation of Si-E bonds by the same well-defined iron pre-catalyst has been discovered by RW.1 The only by-product from dehydrocoupling is H2 and this methodology has been extended to depolymerisation of poly(silazanes). The chemistry is believed to proceed via several iron-hydride intermediates, which SK has used as catalysts for new synthetic methods.2
This PhD builds upon RW’s expertise in iron catalysed main group-main group bond synthesis and experience of polymer chemistry and SK’s expertise in iron-hydride chemistry, mechanisms and electrochemistry. Specifically, this PhD seeks to:
1. Use iron-catalysed dehydrocoupling to transform PMHS into novel poly(siloxysilazanes) and test their physical (RW) and electronic (SK) properties.
2. Determine whether more efficient dehydrocoupling and depolymerisation can take place with more easily prepared, simple iron-hydrides (SK)
3. Determine whether more efficient depolymerisation can take place with more readily accessible, environmentally benign boranes or borohydrides (SK)
4. Investigate uses for depolymerisation monomers of the form R2N-BR2 to prepare valuable heteroatom rich building blocks (RW).3

Sustainability is built into this project from first principles: iron catalyst, hydrogen gas release, atom economy.
Circular technologies are addressed through a cradle-to-grave-to-cradle approach: new materials with applications, which can then be recycled and the building blocks or monomers reused or repurposed.
The collaborative and training-based approach to this PhD is intrinsic to the project, with the student spending the beginning and end of their PhD at Bath developing experience in polymer synthesis and analysis, and the middle portion at Monash developing iron-hydride chemistry and electrochemistry techniques.


Application process

We invite applications from Science and Engineering graduates who have, or expect to obtain, a first or upper second class degree and have a strong interest in Sustainable & Circular Technologies.

You MUST express interest for three projects in order of preference – you can see all projects here: https://www.csct.ac.uk/bath-monash-global-phd-programme/ . Please submit your application at the Home institution of your preferred project (‘Home’ institution details can be found in the project summary). However, please note that you are applying for a joint PhD programme and applications will be processed as such.

University of Bath

Please submit your application through the following link: https://www.csct.ac.uk/bath-monash-global-phd-programme/
Please make sure to mention in the “finance” section of your application that you are applying for funding through the joint Bath/Monash PhD programme for your specified projects.
In the “research interests” section of your application, please name the three projects you are interested in and rank them in order of preference. Please also include the names of the Bath lead supervisors.

Monash University

Expressions of interest (EoI) can be lodged through https://www.monash.edu/science/bath-monash-program. The EoI should provide the following information:
CV including details of citizenship, your Official Academic Transcripts, key to grades/grading scale of your transcripts, evidence of English language proficiency (IELTS or TOEFL, for full requirements see: https://www.monash.edu/graduate-research/faqs-and-resources/content/chapter-two/2-2), and two referees and contact details (optional). You must provide a link to these documents in Section 8 using Google Drive (Instructions in Section 8).

Funding Notes

Bath Monash PhD studentships include tuition fee sponsorship and a living allowance (stipend) for the course duration (up to 42 months maximum). Note, however, that studentships for Bath-based projects will provide cover for UK/EU tuition fees ONLY. Non-Australian nationals studying in Australia will be required to pay their own Overseas Student Health Cover (OSHC).
Additional and suitably qualified applicants who can access a scholarship/studentship from other sources will be also considered.

References

1. D. Gasperini, S. E. Neale, A. K. King, S. A. Macgregor and R. L. Webster, unpublished. For previous research involving iron catalysed amine-borane formation see: N. T. Coles, M. F. Mahon and R. L. Webster, Organometallics, 2017, 36, 2262-2268; M. Espinal-Viguri, S. E. Neale, N. T. Coles, S. A. Macgregor and R. L. Webster, J. Am. Chem. Soc., 2019, 141, 572-582.
2. S. H. Kyne, M. Clémancey, G. Blondin, E. Derat, L. Fensterbank, A. Jutand, G. Lefèvre and C. Ollivier, Organometallics, 2018, 37, 761 771.
3. M. Mesgar, J. Nguyen-Le and O. Daugulis, J. Am. Chem. Soc., 2018, 140, 13703-13710; D.-W. Gao, Y. Gao, H. Shao, T.-Z. Qiao, X. Wang, B. B. Sanchez, J. S. Chen, P. Liu and K. M. Engle, Nature Catalysis, 2019, DOI: 10.1038/s41929-019-0384-6.

How good is research at University of Bath in Chemistry?

FTE Category A staff submitted: 33.10

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