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Triazolium ionic liquid crystals as structured electrolytes and membranes

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  • Full or part time
    Prof D W Bruce
    Dr J Slattery
  • Application Deadline
    Wednesday, January 09, 2019

Project Description

Ionic liquids (ILs) are molten salts with melting temperatures <100 °C. They have received much attention over the last ten years or so because of their interesting, and sometimes unique, combination of physical properties and because of their wide range of potential applications: e.g. from potentially green solvent systems to electrolytes in batteries and solar cells, and in biomass processing. An intriguing aspect of ILs is the fact that many display nano-scale ordering, driven by the phase separation of polar (ionic) and non-polar (aliphatic) parts of the constituent ions. Careful design of the constituent IL ions can then lead to materials displaying liquid-crystalline mesophases and there is scope for the formation of other self-organised structures (e.g. micelles). The ability to control self-organisation in ILs offers huge potential to tune their properties and may allow ILs to be used as liquid nano-reactors, as 1D- or 2D-conducting electrolytes or in gas storage/separation.

The present project capitalises on the design of new ionic liquid crystals (Chem. Commun. 2018, 54, 9965) based on a 1,2,4-triazolium cation that contains a perfluorocarbon chain in addition to hydrocarbon chains (the figure opposite shows a schematic diagram illustrating the overall design).. Having established the feasibility of this approach, we now seek to develop the chemistry, in collaboration with the group of Pace and Pibiri in Palermo, Italy, to the preparation of materials with potential applications as anisotropic electrolyes, membrane materials and solvents for chemical reactions.
The overall chemical structure of the target systems is given alongside. The nature of the chemistry requires to incorporation of the perfluorocarbon chains on the triazolium ring and elaboration is achieved by R1 to R3 as well as anion X (e.g. OTf, CnH2n+1OSO3, Tf2N, BF4). Use of polymerizable units at the end of chains reveals the possibility of polymerising the compounds while in the liquid crystal phase, this leading to membrane materials whose properties (e.g. conductivity, oxygen permeability) will be controlled through the nature of the monomer.

The project offers the chance to work in a collaborative fashion between the Bruce and Slattery groups with their expertise in liquid crystals and ionic liquids, respectively. The work is also part of a collaboration with Pace and Pibiri in Palermo, Italy, and 18 months of the project will be spent working there with them. It is a truly multidisciplinary and multinational project (collaboration is likely also with groups in Portugal and Australia) and the student undertaking this work will receive a truly broad-based training.

All research students follow our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills. All research students take the core training package which provides both a grounding in the skills required for their research, and transferable skills to enhance employability opportunities following graduation. Core training is progressive and takes place at appropriate points throughout a student’s higher degree programme, with the majority of training taking place in Year 1. In conjunction with the Core training, students, in consultation with their supervisor(s), select training related to the area of their research.

In the laboratory, the student will learn techniques associated with the preparation and purification of ionic liquid crystals containing long hydrocarbon and fluorocarbon chains, and an aspect of the work will concern in situ polymerisation in liquid crystal phases. The materials will be characterised chemically by 1H, 13{1H} and 19F NMR spectroscopy, mass spectrometry, elemental analysis and single-crystal X-ray diffraction.

Liquid crystal phases will be identified using polarised optical microscopy, while phase transitions are confirmed using complementary differential scanning calorimetry. Structural information in the liquid crystal mesophase comes from small-angle X-ray scattering and it is anticipated that conductivity studies will be carried out to assess potential as electrochemical solvents.

Finally, for students who are interested, the possibility exists to engage with computational approaches, using quantum chemical and atomistic methods to generate complementary data. There is also the chance that the work will demand study using neutron methods using the national facility at the Rutherford Laboratories in Oxfordshire.

The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel: https://www.york.ac.uk/chemistry/ed/. This PhD project is available to study full-time or part-time (50%).

This PhD will formally start on 1 October 2019. Induction activities will start on 30 September.

Funding Notes

Fully funded for 3 years by either the Engineering and Physical Sciences Research Council or a Chemistry Teaching Studentship and cover: (i) a tax-free annual stipend at the standard Research Council rate (£14,777 for 2018-19), (ii) tuition fees at the UK/EU rate, (iii) funding for consumables. You do not need to apply separately for the EPSRC funding. However you need to submit a separate Teaching Studentship application: https://www.york.ac.uk/chemistry/postgraduate/research/teachingphd/
Teaching studentships are available to any student who is eligible to pay tuition fees at the home rate. ESPRC Studentships are available to any student who meets the EPSRC eligibility criteria: https://epsrc.ukri.org/skills/students/help/eligibility/

References

• Applicants should submit an application for a PhD in Chemistry by 9 January 2019
• Supervisors may contact their preferred candidates either by email, telephone, web-chat or in person
• Supervisors may nominate up to two candidates to the assessment panel
• The assessment panel will shortlist candidates for interview from all those nominated
• Shortlisted candidates will be invited to a panel interview at the University of York on 13 or 15 February 2019
• The Awards Panel will award studentships following the panel interviews
• Candidates will be notified of the outcome of the panel’s decision by email

How good is research at University of York in Chemistry?

FTE Category A staff submitted: 47.06

Research output data provided by the Research Excellence Framework (REF)

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