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Title: Supercatalysis by superexchange
Authors: Fletcher, Stephen
Van Dijk, Nicholas J.
Issue Date: 2016
Publisher: American Chemical Society
Citation: FLETCHER, S. and VAN DIJK, N.J., 2016. Supercatalysis by Superexchange. The Journal of Physical Chemistry C, 120 (46), pp 26225–26234.
Abstract: In modern transition state theory, the rate constant for an electron transfer reaction is expressed as the product of four factors: an exponential factor, a pre-exponential factor, an electronic transmission coefficient, and a nuclear transmission coefficient. The activation energy of the reaction manifests inside the exponential factor, and on the conventional view, catalysis occurs by decreasing this activation energy below its catalyst-free value. In the present work we report the discovery of an unusual counter-example in which catalysis occurs by increasing the electron transmission coefficient far above its catalyst-free value. The mechanism involves the formation of a superexchange bridge between an electron donor (a graphite cathode) and an electron acceptor (a pentasulfide ion). The bridge consists of a dz2 orbital inside a cobalt phthalocyanine molecule. The dramatic result is the acceleration of the reduction of pentasulfide ions by more than 5 orders of magnitude compared with the catalyst-free case.
Description: ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Sponsor: This work was sponsored by the EPSRC (UK) Grant Number: EP/M009394/1, “Electrochemical Vehicle Advanced Technology” (ELEVATE). N.J.V.D. also thanks Regenesys Technologies Ltd. for a scholarship.
Version: Published
DOI: 10.1021/acs.jpcc.6b09099
URI: https://dspace.lboro.ac.uk/2134/23355
Publisher Link: http://dx.doi.org/10.1021/acs.jpcc.6b09099
ISSN: 1932-7447
Appears in Collections:Published Articles (Chemistry)

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