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SHINERS for the study of electrochemical and catalytic processes

  • Full or part time
  • Application Deadline
    Monday, June 01, 2020
  • Funded PhD Project (European/UK Students Only)
    Funded PhD Project (European/UK Students Only)

Project Description

The PhD project in partnership with the global science and chemicals company Johnson Matthey (JM) will involve the growth of SHell Isolated Nanoparticles for Enhanced Raman Spectroscopy (SHINERS) and their use in-operando to study electrochemical and catalytic processes.
For electrochemical applications, SHINERS will be deposited onto battery electrode surfaces to study processes occurring during cycling, including surface evolution and degradation. For catalytic applications, metal nanoparticles will be deposited on the SHIN (shell isolated nanoparticles) and these will be used to explore catalyst mechanisms, with aldehyde hydrogenation used as an initial system. Gaining a greater understanding of the reactions and pathways that occur at these interfaces will lead to improved material design and in turn increased yield, efficiency, and durability.
SHINERS is a technique that allows the surface enhanced Raman spectroscopy (SERS) effect to be applied to any surface. A SERS active gold core is coated with an inert shell which prevents the gold core from taking part in reactions. SHIN can be placed onto a surface to greatly enhance their otherwise weak Raman signal and permit the observation of species which cannot otherwise be detected. Furthermore, metal nanoparticles can be grown on the outside of the inert shell of the SHINERS, in this way; the signal from the nanoparticle (catalyst) surface can be enhanced.
For catalysis, an example of a reaction where mechanistic information is lacking is the hydrogenation of α,β-unsaturated aldehydes. Cu and Pt particles are commonly used for their differing selectivity for this reaction, however current mechanistic information mostly comes from theoretical calculations. The hydrogenation of α,β-unsaturated aldehydes will be used as models to study this reaction at elevated temperatures by attaching Cu and Pt particles onto the surface of the SHIN.
In lithium-ion batteries, the processes which occur at the interface between the electrolyte and the electrode surface are crucial in determining the performance of the battery. An example of a particularly important process is that which occurs at the cathode-electrolyte interface, degradation and build-up of material on the surface occurs with cycling. SHINERS is able to observe these changes where Raman spectroscopy alone cannot, and the effect of different cathodes, electrolytes, and voltage profiles can be used to further understand degradation processes.
The student would be trained in core-shell nanoparticle synthesis and characterisation (the synthesis of the SHINERS particles requires precise control to produce particles of the correct size, shell conformity, and shell thickness), Raman spectroscopy, electrochemistry, frontier battery research and catalysis. The student will have the opportunity to be hosted at JM Technology Centre to work alongside JM research scientists developing the chemistry and understanding the mechanistic aspects of battery and catalytic materials.
Applications are encouraged from highly motivated candidates who have, or expect to have, at least a 2:1 degree or equivalent in Chemistry.
Applications should be made as soon as possible but no later than 1st June 2020. Informal enquiries are also encouraged and should be addressed to Professor Laurence Hardwick

To apply for this opportunity, please visit: https://www.liverpool.ac.uk/study/postgraduate-research/how-to-apply/

Funding Notes

The award will pay full tuition fees and a maintenance grant for 3.5 years (currently £14,777 p.a.) and it is anticipated that the successful candidate will start in October 2020. Applications from candidates meeting the eligibility requirements of the EPSRC are welcome – please refer to the EPSRC website.

References

For recent literature examples and background see:
Water Oxidation Intermediates on Iridium Oxide Electrodes Probed by In Situ Electrochemical SHINERS, Chem. Commun., (2020) in press DOI:10.1039/C9CC08284K
Oxygen reactions on Pt{hkl} in a non-aqueous Na+ electrolyte: Site selective stabilization of a sodium peroxy species, Chem. Sci, 10 (2019), 2956-2964 DOI
Shell Isolated Nanoparticles for Enhanced Raman Spectroscopy Studies in Lithium-Oxygen Cells, Faraday Discuss., 205 (2017) 469 DOI
Utilizing In Situ Electrochemical SHINERS for Oxygen Reduction Reaction Studies in Aprotic Electrolytes, J. Phys. Chem. Lett., 7 (2016) 2119 DOI

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