Dr Alex Murray
Dr Alex Murray started his chemistry career at the University of Sheffield, completing an undergraduate degree in 2011. He then moved to the University of Bath, where he carried out his PhD research with Dr Dave Carbery on the utilisation of synthetic catalysts to probe the mechanisms of biological organic redox reactions. He went on to work at the University of Nottingham as a postdoctoral researcher under the direction of Professor Chris Moody; his focus was the design of novel frameworks for library design in medicinal chemistry under the umbrella of the Innovative Medicines Institute ‘European Lead Factory’ programme, an EU-wide academia and industry consortium.
On leaving Nottingham, Alex moved to the USA, obtaining a Dreyfus Postdoctoral Scholarship in environmental chemistry to work with Professor Yogesh Surendranath at the Massachusetts Institute of Technology, where he worked on the mechanisms of electrochemical oxygen reduction, the ability of modified carbon materials to promote thermal catalysis and the use of electrochemical mediators in phase transfer catalysis.
Alex joined the School of Physical Sciences at the University of Kent in May 2018 and is interested in designing organic molecules for electrochemical energy storage.
Kasel, T., Murray, A. and Hendon, C. (2018). Cyclopropenium (C3H3)+ as an Aromatic Alternative A-Site Cation for Hybrid Halide Perovskite Architectures. Journal of Physical Chemistry C [Online] 122:2041-2045. Available at: https://doi.org/10.1021/acs.jpcc.7b11867.
Murray, A. and Surendranath, Y. (2017). Reversing the Native Aerobic Oxidation Reactivity of Graphitic Carbon: Heterogeneous Metal-Free Alkene Hydrogenation. ACS Catalysis [Online] 7:3307-3312. Available at: https://doi.org/10.1021/acscatal.7b00395.Commercially available carbon blacks serve as effective metal-free catalysts for the selective hydrogenation of carbon-carbon
multiple bonds under aerobic conditions using hydrazine as the terminal reductant. The reaction, which proceeds
through a putative diimide intermediate, displays high tolerance to a variety of functional groups, including those sensitive to nucleophilic
displacement by hydrazine, aerobic oxidation, or hydrazine-mediated reduction. Hydrazine chemisorbs strongly to the
carbon surface, attenuating its native oxidative reactivity and allowing for selective hydrogenation. The catalytic sequence established
here effectively umpolungs the reactivity of carbon, thereby enabling the use of this low cost material in selective reduction
Santaclara, J., Olivos-Suarez, A., Gonzalez-Nelson, A., Osadchii, D., Nasalevich, M., van der Veen, M., Kapteijn, F., Sheveleva, A., Veber, S., Fedin, M., Murray, A., Hendon, C., Walsh, A. and Gascon, J. (2017). Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysis. Chemistry of Materials [Online] 29:8963-8967. Available at: https://doi.org/10.1021/acs.chemmater.7b03320.
Ricke, N., Murray, A., Shepherd, J., Welborn, M., Fukushima, T., Van Voorhis, T. and Surendranath, Y. (2017). Molecular-Level Insights into Oxygen Reduction Catalysis by Graphite-Conjugated Active Sites. ACS Catalysis [Online] 7:7680-7687. Available at: https://doi.org/10.1021/acscatal.7b03086.Using a combination of experimental and computational investigations we assemble a consistent mechanistic model
for the oxygen reduction reaction (ORR) at molecularly well-defined graphitic-conjugated catalyst (GCC) active sites featuring arylpyridinium
moieties (N+-GCC). ORR catalysis at glassy carbon surfaces modified with N+-GCC fragments displays near first order
dependence in O2 partial pressure and near zero order dependence on electrolyte pH. Tafel analysis suggests an equilibrium oneelectron
transfer process followed by a rate-limiting chemical step at modest overpotentials that transitions to a rate-limiting electron
transfer sequence at higher overpotentials. Finite-cluster computational modelling of the N+-GCC active site reveals preferential O2
adsorption at electrophilic carbons alpha to the pyridinium moiety. Together, the experimental and computational data indicate that
ORR proceeds via a proton-decoupled O2 activation sequence involving either concerted or step-wise electron transfer and adsorption
of O2, which is then followed by a series of electron/proton transfer steps to generate water and turnover the catalytic cycle. The
proposed mechanistic model serves as a roadmap for the bottom-up synthesis of highly active N-doped carbon ORR catalysts.
Murray, A., Frost, J., Hendon, C., Molloy, C., Carbery, D. and Walsh, A. (2015). Modular design of SPIRO-OMeTAD analogues as hole transport materials in solar cells. Chemical Communications [Online] 51:8935-8938. Available at: https://doi.org/10.1039/C5CC02129D.We predict the ionisation potentials of the hole-conducting material SPIRO-OMeTAD and twelve methoxy isomers and polymethoxy derivatives. Based on electronic and economic factors, we identify the optimal compounds for application as p-type hole-selective contacts in hybrid halide perovskite solar cells.
Murray, A., Dowley, M., Pradaux-Caggiano, F., Baldansuren, A., Fielding, A., Tuna, F., Hendon, C., Walsh, A., Lloyd-Jones, G., John, M. and Carbery, D. (2015). Catalytic amine oxidation under ambient aerobic conditions: mimicry of monoamine oxidase B. Angewandte Chemie International Edition [Online] 54:8997-9000. Available at: https://doi.org/10.1002/anie.201503654.The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase?B activity.