Methane is an inert greenhouse gas that warms up the atmosphere, yet there are very few practical processes for converting this natural gas directly into more valuable products. Therefore, methane is often wasted and over 90% is simply burned. The challenge of controlled methane activation is caused by the inert character of the methane molecule; it is non-polar with a high C–H bond strength (BDE = 105 kcal/mol), a high ionization potential (12.6 eV) and low proton affinity (132 kcal/mol). These properties generally result in harsh reaction conditions, which are undesired while producing more reactive products compared to the starting material.
New processes for methane upgrading to platform molecules are therefore urgently needed, which is why we át the Van't Hoff Institute for Molecular Sciences (HIMS) of the Faculty of Science are seeking a PhD candidate who is interested in exploring new methods for the activation and functionalization of inert C–H bonds using main-group Lewis acids and bases.
In particular, we are interested in Lewis acid/base combinations that can form charge-transfer complexes that are susceptible to thermal or photo-induced single-electron transfer enabling the formation of radical ion pairs. We set out to target and generate such long-lived radical ion pairs and then explore their subsequent reactivity. To reduce synthetic chemistry’s dependence on noble, scarce and toxic elements, we aim at developing systems based on abundant and benign main-group elements. By doing so, this project sets out to develop a new research domain: main-group (photo)redox chemistry and -catalysis, which we will explore for the homolytic bond activation and subsequent functionalization of the greenhouse gas methane.
What are you going to do?
You are expected to:
- be active in the fundamental research of our sustainable main-group chemistry group, publishing in high level international journals, presenting at leading conferences and supervising BSc and MSc students;
- study the generation of main-group radicals and radical ion pairs using single-electron transfer experimentally and computationally;
- study the reactivity of main-group radicals promoting the homolytic cleavage of inert C–H bonds experimentally and computationally;
- design efficient functionalization/coupling protocols enabling the use of methane as feedstock.
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