PhD in Programming Copper–Zinc Heteromultimetallic Complexes for CO2 Reduction at University of Bath

Overview of the Research:

Developing useful applications for carbon dioxide (CO₂) is a high economic priority with important global implications. An exciting potential application is in the development of liquid fuels based on CO₂ reduction, an attractive means to lower dependence on oil reserves and mitigate climate change. One such liquid fuel is methanol, produced by the reaction of CO₂ and H₂ with H₂O as the only side product.

A heterogeneous multimetallic catalyst comprised of a mixture of copper and zinc-oxide nanoparticles with an alumina support (Cu/ZnO/Al₂O₃) is the only commercially viable system capable of converting CO₂-to-methanol. The role of each component in the Cu/ZnO/Al₂O₃ catalyst remains highly debated. Recently, it has been shown that increasing the contact area between Cu and Zn species is crucial for maximising product formation. The chemical origin of this special synergy between copper and zinc is yet to be elucidated, but in heterogeneous systems the contributing factors are hard to deconvolute.

One approach to model the Cu–Zn active site involves preparing homogeneous complexes with multiple copper and zinc centres in close proximity. These nanoclusters offer new opportunities to control and study more complicated active sites. There are limited reports on the application of well-defined nanoclusters in catalysis due to the challenges associated with their controlled synthesis, which are often highly specific protocols that rely heavily on serendipity. We will employ a novel computational approach that uses machine learning to develop ligand designs. These judiciously designed ligands will act as templating platforms allowing us to access nanoclusters of any size, shape and connectivity, ultimately allowing their systematic study. Initial results using a ligand design with a central linker unit flanked by terminal binding groups has allowed us to access unusual Zn—Cu—Zn motifs which are capable of partial CO₂reduction.

With the aim of understanding the critical parameters that control industrially relevant CO₂ hydrogenation to methanol, we will use homogeneous nanoclusters to model the reactions at the surface of the heterogeneous Cu/ZnO/Al₂O₃ catalyst. We will study the reactivity of proposed key intermediates during CO₂-to-methanol catalytic cycle, gaining hitherto inaccessible mechanistic insight into the roles of each metal.

Project keywords: carbon dioxide, hydrogenation, nanocluster catalysts, computer-aided design, mechanistic understanding

Candidate Requirements:

Applicants should hold, or expect to receive, a First Class or good Upper Second Class UK Honours degree (or the equivalent) in a relevant subject. A master’s level qualification would also be advantageous.

Experience in Schlenk-line/glovebox techniques and/or computational chemistry is desirable but not required.

Non-UK applicants must meet the programme’s English language requirement by the application deadline.

For more information and to apply visit https://www.findaphd.com/phds/project/programming-copper-zinc-heteromultimetallic-complexes-for-co2-reduction/?p175932