Detection of reaction intermediates in catalytic reactions by microwave perturbed electron paramagnetic resonance (EPR) spectroscopy
This research project is in competition for funding with one or more projects available across the EPSRC Doctoral Training Partnership (DTP). Usually the projects which receive the best applicants will be awarded the funding. Find out more information about the DTP and how to apply.
Application deadline: 31 July 2018 (We reserve the right to close applications early should sufficient applications be received.)
Start date: 1 October 2018
Microwave (MW) heating continues to grow as an important enabling technology, primarily owing to the proven capability of MWs to speed up the rate of chemical reactions.
However, it is surprising that the precise molecular explanation of how MWs heat liquids and solids remains poorly understood. Understating this is vitally important owing to the growing use of MW reactors for enhancing the rates of chemical reactions.
This is particularly relevant in catalysis, where very large rate enhancements can be achieved using MW-heating. Another key advantage of MW-heating for catalysis is the almost instantaneous and rapid heating of the sample. Thus, whilst MW-heating is very important in reaction rate enhancement, particularly in catalysis, our understanding of the MW-specific enhancement or heating effects are poorly understood.
At the same time, the ability to rapidly heat a chemical system can also be exploited for the study of reaction mechanisms. The chemical or conformational equilibrium can be easily perturbed and shifted in either direction, when a stress is applied. This stress may involve a change in concentration, pressure or temperature.
The rate of change from the old to the new equilibrium will depend on the rate constant for the forward and reverse reactions or the conformational change, so that analysis of this rate is extremely informative in chemical kinetics and dynamics. Rapid heating by microwaves (creating a T-Jump) using a suitable resonator, could therefore be used as a novel means of studying reaction kinetics and dynamics.
Project aims and methods
In this project we will develop a unique dual-mode electron paramagnetic resonance (EPR) based reactor-resonator.
You will build the device specifically to demonstrate its utility for investigating the fundamental nature of how MW heating can influence the rate and product distribution in catalysis.
This will follow how the reaction pathways are altered by T-jump heating to fundamentally understand how MW-specific effects lead to enhancement of photogenerated radical lifetimes and to indirectly understand how MWs heating of liquids and solids occurs.