Catalyzing and Controlling Chemical Reactions with Electric Fields

Speaker: Professor Michelle L. Coote
Institute: Australian National University
Country: Australia
Speaker Link:

Michelle L. Coote

ARC Centre of Excellence for Free-Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra ACT 2601, Australia

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Chemists appreciate that the rate of redox reactions can be manipulated by means of an electrical potential gradient. However, it was only in 2016 that it was shown that an external electric field can also be used to catalyze non-redox reactions, thereby opening up a new dimension to chemical catalysis [1]. So-called electrostatic catalysis arises because most chemical species have some degree of polarity and so can be stabilized by an appropriately aligned electric field; when this occurs to a greater extent in transition states compared with reactants, reactions are catalyzed [2]. However, by their nature such effects are highly directional and so implementing them in practical chemical systems is problematic. We have been using a combination of theory and experiment to explore various solutions to this problem ranging from the single molecule level through to the macro-scale [3]. In the course of this work, we have discovered interesting electrostatic effects on electrochemistry and useful electrochemically triggered reactions that are aided by the electric fields in the double layer [4]. These have caused us to re-think some of the assumptions made when using theory to predict redox potentials, among other things. This talk will outline our experimental and theoretical results [1,4,5] and discuss the prospects for electrostatic catalysis. It will also highlight some of the modelling challenges encountered when studying these interesting chemical systems.

Key References

[1] Aragones, Haworth, Darwish, Ciampi, Bloomfield, Wallace, Diez-Perez, Coote, Nature, 2016, 531, 88-91.

[2] Shaik, Mandal, Ramanan, Nat. Chem. 2016, 8, 1091-1098 & Chem. Soc. Rev., 2018,47, 5125-5145.

[3] Ciampi Darwish, Aitken, Diez-Perez, Coote, Chem. Soc. Rev., 2018, 47, 5146-64.

[4] Zhang, Laborda, Darwish, Noble, Tyrell, Pluczyk, Le Brun, Wallace, Gonzalez, Coote, Ciampi, J. Am. Chem. Soc., 2018, 140, 766.

[5] Gryn’ova, Marshall, Blanksby, Coote, Nat. Chem., 2013, 5, 474; Gryn’ova, Coote, J. Am. Chem. Soc, 2013, 135, 15392; Klinska, Smith, Gryn’ova, Banwell, Coote, Chem. Sci., 2015, 6, 5623; Gryn'ova, Smith, Coote, Phys. Chem. Chem. Phys., 2017, 19, 22678; Aitken, Coote, Phys. Chem. Chem. Phys., 2018, 20, 10671.

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