Promotion of the Oxidation of Carbon Monoxide at Stepped Platinum Single-Crystal Electrodes in Alkaline Media by Lithium and Beryllium Cations

Stoffelsma, Chantal; Rodríguez, Paramaconi; Garcı́a, Gonzalo; Garcı́a-Aráez, Nuria; Strmčnik, Dušan; Marković, Nenad M.; Koper, Marc T. M.

doi:10.1021/ja106389k

Cited by 137 publications

(130 citation statements)

References 28 publications

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“…[8][9][10][11][12][13] Similar effects have also been observed for the electrochemical reduction of oxygen, the oxidation of hydrogen, and the oxidation of low molecular weight alcohols. [14][15][16][17][18] For Ag and Hg, which are selective for CO 2 reduction to carbon monoxide (CO) and formate anions (HCOO -), respectively, increasing the alkali metal cation size increases the rates of formation of these products. 8,10,11 For Cu, increasing alkali metal size leads to higher selectivities to C 2 products, e.g., ethylene and ethanol.…”

Section: Introductionmentioning

confidence: 99%

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

et al. 2017

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The electrochemical reduction of CO 2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO 2 . Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably for HCOO The observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.

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Section: Introductionmentioning

confidence: 99%

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

et al. 2017

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“…Such conclusion comes from different studies using basal planes and stepped Pt electrodes [6]. In addition, it is also well-known that the CO electro-oxidation reaction on platinum electrodes strongly depends on the surface composition and the electrolyte solution (acidic or alkaline) [7][8][9], as well as the nature of both cations [10] and anions [11]. For Pt(s)-[(n-1)(111)×(110)] electrodes in acid medium, potentiostatic CO stripping experiments at full coverage are characterized by the presence of a single CO oxidation peak [2,6,12].…”

Section: Introductionmentioning

confidence: 99%

On the behavior of CO oxidation on shape-controlled Pt nanoparticles in alkaline medium

Farias

Vidal‐Iglesias

Solla-Gullón

et al. 2014

Journal of Electroanalytical Chemistry

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In this work, the behavior of the CO electro-oxidation reaction on shape-controlled Pt nanoparticles in alkaline medium was examined in order to understand the effect of the surface structure on this reaction. A series of experiments using Pt nanoparticles of different surface structures/shapes was used and the results obtained were compared with the previous knowledge gained from stepped platinum single crystal electrodes. Independently of the preferential orientation of the nanoparticles, the CO oxidation voltammetry exhibits two main peaks: one at ca. 0.56-059 V and the second one at 0.66 -0.67 V, being the intensity of the peaks dependent on the shape of the nanoparticle. These two peaks have been assigned to the oxidation of CO on the (111) terraces and on the rest of the sites, respectively. The appearance of two differentiated peaks reveals that these (111) terraces and the rest of the sites on the nanoparticle surface behave independently of the presence of the other type of sites, that is, they are not connected. The results are discussed considering the effects of the surface mobility of CO and of the OH adsorption properties on the different sites in the oxidation peaks.

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“…These differences were demonstrated by Koper and his co-workers for stepped surfaces containing (111) terrace sites. [15][16][17][18][19] In alkaline media, several peaks appear for the oxidation of CO on those surfaces and a prewave is always present. In general, two main peaks (aside from the pre-wave) are observed in the voltammetry for stepped surfaces with (111) terraces.…”

Section: Introductionmentioning

confidence: 99%

Influence of the CO Adsorption Environment on Its Reactivity with (111) Terrace Sites in Stepped Pt Electrodes under Alkaline Media

et al. 2014

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The effect of the electrode potential in the reactivity of platinum stepped single crystal electrodes with (111) terraces towards CO oxidation has been studied. It is found that the CO adlayer is significantly affected by the potential at which the adlayer is formed. The electrochemical and FTIR experiments show that adsorbed CO layer formed in acidic solution at ~0.03 V vs. SHE is different from that formed at -0.67 V vs. SHE in alkaline solutions. The major effect of the electrode potential is a change in the long-range structure of CO adlayer. The adlayer formed in alkaline media presents a higher number of defects. These differences affect the onset and peak potential for CO stripping experiments. The stripping voltammogram for the adlayer formed at -0.67 V vs. SHE always shows a pre-wave and the peak potential is more negative than that observed for the adlayer formed at 0.03 V vs. SHE. This means that the apparent higher activity for CO oxidation observed in alkaline media is a consequence of the different CO adlayer structure on the (111) terrace, and not a true catalytic effect. The different behavior is discussed in terms of the different mobility of CO observed depending on the electrode potential. Also, the FTIR frequencies are used to estimate the pzc (potential of zero charge) for the Pt(111) electrode covered with a CO adlayer.

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Promotion of the Oxidation of Carbon Monoxide at Stepped Platinum Single-Crystal Electrodes in Alkaline Media by Lithium and Beryllium Cations

Cited by 137 publications

References 28 publications

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide

On the behavior of CO oxidation on shape-controlled Pt nanoparticles in alkaline medium

Influence of the CO Adsorption Environment on Its Reactivity with (111) Terrace Sites in Stepped Pt Electrodes under Alkaline Media

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