Vol.:(0123456789)
Topics in Current Chemistry (2019) 377:5
https://doi.org/10.1007/s41061-018-0228-x
1 3
REVIEW
Determination of Specific Electrocatalytic Sites
in the Oxidation of Small Molecules on Crystalline Metal
Surfaces
Manuel J. S. Farias
1
· Juan M. Feliu
2
Received: 27 August 2018 / Accepted: 26 December 2018 / Published online: 10 January 2019
© Springer Nature Switzerland AG 2019
Abstract
The identification of active sites in electrocatalytic reactions is part of the elucidation of mechanisms of catalyzed reactions on solid surfaces. However, this is not an
easy task, even for apparently simple reactions, as we sometimes think the oxidation
of adsorbed CO is. For surfaces consisting of non-equivalent sites, the recognition
of specific active sites must consider the influence that facets, as is the steps/defect
on the surface of the catalyst, cause in its neighbors; one has to consider the electrochemical environment under which the “active sites” lie on the surface, meaning that
defects/steps on the surface do not partake in chemistry by themselves. In this paper,
we outline the recent efforts in understanding the close relationships between sitespecific and the overall rate and/or selectivity of electrocatalytic reactions. We analyze hydrogen adsorption/desorption, and electro-oxidation of CO, methanol, and
ammonia. The classical topic of asymmetric electrocatalysis on kinked surfaces is
also addressed for glucose electro-oxidation. The article takes into account selected
existing data combined with our original works.
Keywords Electrocatalysis · Single crystal surfaces · Active sites · Structure
sensitivity · Asymmetric electrocatalysis
* Juan M. Feliu
juan.feliu@ua.es
1
Departamento de Química, Universidade Federal do Maranhão, Avenida dos Portugueses, 1966,
São Luís, Maranhão CEP 65080-805, Brazil
2
Instituto de Electroquímica, Universidad de Alicante Ap. 99, E-03080 Alicante, Spain
Reprinted from the journal
79
Chapter 3 was originally published as Farias, M. J. S. & Feliu, J. M. Topics in Current Chemistry (2019)
377: 5. https://doi.org/10.1007/s41061-018-0228-x.
Topics in Current Chemistry (2019) 377:5
https://doi.org/10.1007/s41061-018-0228-x
1 3
REVIEW
Determination of Specific Electrocatalytic Sites
in the Oxidation of Small Molecules on Crystalline Metal
Surfaces
Manuel J. S. Farias
1
· Juan M. Feliu
2
Received: 27 August 2018 / Accepted: 26 December 2018 / Published online: 10 January 2019
© Springer Nature Switzerland AG 2019
Abstract
The identification of active sites in electrocatalytic reactions is part of the elucidation of mechanisms of catalyzed reactions on solid surfaces. However, this is not an
easy task, even for apparently simple reactions, as we sometimes think the oxidation
of adsorbed CO is. For surfaces consisting of non-equivalent sites, the recognition
of specific active sites must consider the influence that facets, as is the steps/defect
on the surface of the catalyst, cause in its neighbors; one has to consider the electrochemical environment under which the “active sites” lie on the surface, meaning that
defects/steps on the surface do not partake in chemistry by themselves. In this paper,
we outline the recent efforts in understanding the close relationships between sitespecific and the overall rate and/or selectivity of electrocatalytic reactions. We analyze hydrogen adsorption/desorption, and electro-oxidation of CO, methanol, and
ammonia. The classical topic of asymmetric electrocatalysis on kinked surfaces is
also addressed for glucose electro-oxidation. The article takes into account selected
existing data combined with our original works.
Keywords Electrocatalysis · Single crystal surfaces · Active sites · Structure
sensitivity · Asymmetric electrocatalysis
* Juan M. Feliu
juan.feliu@ua.es
1
Departamento de Química, Universidade Federal do Maranhão, Avenida dos Portugueses, 1966,
São Luís, Maranhão CEP 65080-805, Brazil
2
Instituto de Electroquímica, Universidad de Alicante Ap. 99, E-03080 Alicante, Spain
Reprinted from the journal
79
Chapter 3 was originally published as Farias, M. J. S. & Feliu, J. M. Topics in Current Chemistry (2019)
377: 5. https://doi.org/10.1007/s41061-018-0228-x.