Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes
Articolo
Data di Pubblicazione:
2014
Citazione:
Uncovering the Missing Link between Molecular Electrochemistry and Electrocatalysis: Mechanism of the Reduction of Benzyl Chloride at Silver Cathodes / O.V. Klymenko, O. Buriez, E. Labbé, D.P. Zhan, S. Rondinini, Z.Q. Tian, I. Svir, C. Amatore. - In: CHEMELECTROCHEM. - ISSN 2196-0216. - 1:1(2014 Jan), pp. 227-240. [10.1002/celc.201300101]
Abstract:
Herein, the traditional views that contrast the important areas
of electrocatalysis and molecular electrochemistry are challenged.
By extending Laviron’s seminal concept, we show that
these two domains only represent idealized limits of a much
broader continuum. More importantly, we show that electrochemical
systems that apparently behave experimentally as if
under diffusion control (i.e. systems that obey the founding
molecular electrochemistry paradigm) may be controlled by
electrocatalytic steps, that is, in which the activation of electroactive
substrates exclusively occurs through adsorbed intermediates.
This analysis is supported through quantitative experimental
and theoretical investigations on the reduction of
benzyl chloride at silver electrodes. At silver cathodes, the reduction
wave of benzyl chloride as monitored at the usual
scan rates is dramatically shifted to more positive potentials by
about 0.5 V versus that at inert (e.g. glassy carbon) electrodes.
This approach, which is based on the use of fast-scan cyclic
voltammetry and simulations (KISSA-1D), combined with our
previous results from surface-enhanced Raman spectroscopy
(SERS) and density functional theory (DFT) analysis, allow us to
fully unravel the mechanistic origin of this dramatic effect and
quantitatively validate this mechanism, which has eluded
many research groups until now. In practice, this example provides
a missing link between the traditional areas of electrocatalysis
and molecular electrochemistry. Furthermore, it bridges
the chemical areas of organometallic/inorganic catalysis and
electrochemical activation by showing that the inner-sphere
concept, as developed by Taube and Myers for inorganic reactions,
applies perfectly to electrochemical reactions of molecular
substrates
Tipologia IRIS:
01 - Articolo su periodico
Elenco autori:
O.V. Klymenko, O. Buriez, E. Labbé, D.P. Zhan, S. Rondinini, Z.Q. Tian, I. Svir, C. Amatore
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