The DReaM-Machine: Operando Investigation and Self-Optimization of Homogeneous Catalysis by Orthogonal Real-time Spectroscopy

Supervisory team:

Lead supervisor: Dr Ulrich Hintermair
http://www.bath.ac.uk/chemistry/contacts/academics/ulrich_hintermair/
Co-supervisors: Dr John Lowe (Bath) and Dr Ian Clegg (Bruker UK)

Context:

Catalysis is a hugely important technology for the chemical industry in supplying society with raw materials and energy. 80 - 90 % of all man-made materials produced go through at least one catalytic step, and catalytic technologies are key to a more sustainable future. We use molecularly defined metal complexes as catalysts for a range of chemical transformations and chemical energy conversion. A central theme of our work is thorough mechanistic and kinetic understanding of the catalytic system, for which we employ (and as in this project, sometimes develop) techniques that allow studying catalysts “at work”.

Project description:

The effective development and optimization of chemical reactions is often hampered by limited insight into the mechanism and kinetics. For example, rational catalyst development is only possible through a thorough understanding of catalyst activation and de-activation mechanisms, potential resting or dormant states, and the kinetics of the productive cycle (i.e. rate-limiting steps). While rather laborious techniques are available to investigate these aspects separately there is no readily applicable technique that may be used universally in early stages of reaction development.

This project forms part of the development of an integrated setup using a range of complementary spectroscopic and chromatographic techniques to follow catalytic liquid phase reactions in real time. Our unique combination of NMR, EPR, UV-vis, HPLC, and mass spectrometry in a continuous-flow setup promises unprecedented kinetic and mechanistic insight into complex catalytic transformations by providing a comprehensive map of the entire reaction network, and the candidate will be expected to play a central role in its development. Particular emphasis will lie on the identification and quantification of catalyst intermediates at the same time for extracting experimental (kinetic) evidence on the mechanistic relevance of possible intermediates.

In addition, on-the-fly analysis of the data collected by the instruments may be used for regulating and optimizing reactions conditions using feedback loops with evolutionary algorithms. The power of such “synthesis machines” or “robo-chemists” has recently been demonstrated in organic synthesis, and adaption to homogeneous catalysis development can be expected to similarly transformational.

Outline work program:

Y1: Cross-validation of the different techniques and development of effective and robust experimental protocols using a set of model reactions, with particular attention to flow effects on quantitative analysis. Kinetic and mechanistic validation of the model systems (examples include Ru-catalysed olefin metathesis, Pd-catalysed cross-couplings, Rh-catalysed hydrogenations, Ir-catalysed H2-borrowing chemistry)

Y2: Software integration of the various techniques, unifying instrument control and automating data analysis. Deeper mechanistic studies on new reactions developed in other projects in our lab (the degree of involvement will depend on the candidate’s background and motivation).

Y3: Self-regulation of homogeneously catalysed reactions in continuous-flow mode to enable self-optimization of reaction conditions for max. performance (‘application mode’) and automation of kinetic interrogation (‘mechanistic mode’).

Essential skills and interests: physical chemistry (kinetics, mechanisms, spectroscopy), chemical engineering (flow measurement and control).

Desirable skills and interests: inorganic chemistry (organometallics, TM catalysis), software development (regulation, automation).

The successful candidate will become part of our reaction monitoring team currently consisting of one 2nd year PhD student, one 1st year PhD student and our newly appointed instrument specialist for the DReaM facility. This project is co-sponsored by Bruker UK, offering ample project support and possibilities for industrial training. Other industrial partners of the DReaM facility are available for support with software integration aspects.

Motivated applicants with a solid background in chemistry or chemical engineering (1st or 2nd degree) are encouraged to get in touch with the supervisor to discuss further details.

As part of a thriving multi-disciplinary research group you will gain excellent training in applied homogeneous catalysis and spectroscopy. In addition, the University’s Researcher Development Unit offers a variety of PG skill courses to turn you into a well-rounded independent researcher fit for a variety of career options.

Anticipated start date: 2 October 2017.

Applications may close earlier than the advertised deadline if a suitable candidate is found; therefore, early application is recommended.