Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces


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 site-specific 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.

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Fig. 1
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Fig. 3

adapted from the American Chemical Society [49] and Elsevier [25] with permission

Fig. 4

adapted from the Royal Society of Chemistry [50] with permission

Fig. 5

adapted from the American Chemical Society [49] with permission

Fig. 6

modified Pt(111) electrode in 0.1 M HClO4. a Cyclic voltammograms (methanol electro-oxidation + blank cyclic voltammograms). b, c In situ FTIR spectra. The spectra in the frequency region between 2500 and 2200 cm−1 (b) were calculated using the spectrum at 0.05 VRHE as reference, while the spectra in the frequency region between 2200 and 1800 cm−1 (c) were calculated using the spectrum at 1.30 VRHE as reference. The original figures were modified. Data are reproduced from the American Chemical Society [70] with permission

Fig. 7

adapted from the American Chemical Society [70] with permission

Fig. 8
Fig. 9

modified and reproduced from Elsevier [84] with permission

Fig. 10

adapted from Springer Nature [96] with permission

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M.J.S.F. is grateful to PNPD/CAPES (Brazil). J.M.F. thanks the MCINN (FEDER, Spain) project-CTQ-2016-76221-P.

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Correspondence to Juan M. Feliu.

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This article is part of the Topical Collection “Electrocatalysis”; edited by Minhua Shao.

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Farias, M.J.S., Feliu, J.M. Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces. Top Curr Chem (Z) 377, 5 (2019).

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  • Electrocatalysis
  • Single crystal surfaces
  • Active sites
  • Structure sensitivity
  • Asymmetric electrocatalysis