Interaction of water with methanesulfonic acid on Pt single crystal electrodes

Sandoval, Andrea P.; Suárez-Herrera, Marco F.; Climent, Vı́ctor; Feliu, Juan M.

doi:10.1016/j.elecom.2014.11.007

Cited by 13 publications

(8 citation statements)

References 30 publications

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“…As highlighted before [13,15], liquid water structure modifies the OH ads adsorption dynamics, which in turn changes the adlayer structure and composition [19,22], and the water dipole orientation at the polarized water/electrode interface [6], affecting the structure of the electric double layer (EDL). Supporting the first case, ORR activities, evaluated as current densities at 0.9 V, of Pt single crystals in acidic media have been correlated with the shift in OH-binding energy, ΔG OHads , on {111} terraces, when a reference charge of 40 µC cm -2 has been transferred, resulting in an volcano type curve [28].…”

Section: Resultsmentioning

confidence: 99%

“…In this sense, the electrode activity in the presence of methanesulfonic acid (MTSA) is evaluated. This organic acid is chosen because despite its promoting effect on the equilibrium that exists at room temperature between ice-like and non ice-like water structure, reflected in noticeable changes in the shape of the characteristic voltammetric profile of Pt(111) in non-adsorbing electrolytes, it does not specifically adsorb on platinum surfaces [13]. Therefore, any change in the ORR dynamic in presence of this acid can be attributed to changes in the water interfacial structure and not to a poisoning of active sites by sulfonic anions.…”

Section: Introductionmentioning

confidence: 99%

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Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

et al. 2016

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Most of electrocatalytic reactions occur in an aqueous environment. Understanding the influence of water structure on reaction dynamics is fundamental in electrocatalysis. In this work, the role of liquid water structure on the oxygen reduction at Pt(111) electrode is analyzed in methanesulfonic (MTSA) and perchloric acids. This is because different anions can exert a different influence on liquid water structure. Results reveal a lower electrode activity in MTSA than in HClO 4 solutions and they are discussed in light of anion influence in water structural ordering. From them, the existence of an outer-sphere step in the ORR mechanism is proposed

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

et al. 2016

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“…Such effect was rationalized considering the capacity of some anions to induce water ordering whereas other anions cause disordering in the structure of water [44,45]. Thus, the type of anion present in the electrolyte could have a great influence in the interfacial properties of Metal|Solution interfaces even in the absence of adsorption [46]. In particular, fluoride is an anion expected to favour the formation of structured water [35,43].…”

Section: Theoretical Considerationsmentioning

confidence: 99%

Study of the Pt (111) | electrolyte interface in the region close to neutral pH solutions by the laser induced temperature jump technique

Sebastián

Martínez‐Hincapié

Climent

et al. 2017

Electrochimica Acta

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The laser-induced temperature jump method is used to determine the potential of maximum entropy (pme) of a Pt(111) single crystal electrode in contact with an aqueous solution, in a wide pH range and in the absence of specifically adsorbed anions. For this purpose, buffer solutions composed of a mixture of NaF and HClO4 are used. The results are compared with those from non-buffered perchlorate solutions. The use of the NaF/HF buffer allows extending the pH range from 3 to 6, approaching the situation of a neutral pH. Laser experiments show that the pme appears located at nearly the same potential position in the whole pH range between 3 and 6. This value is around 300 mV vs SHE, in agreement with previous works. Moreover, the potential response to the fast thermal perturbation at high potentials, above the pme, indicates the presence of a slower contribution, resulting in a bipolar, non-monotonous, profile. Such behaviour is strongly affected by the presence of fluoride anion and/or hydrofluoric acid, thus evidencing a strong structural effect on interfacial water from these species. These results bring some light to the understanding of the interfacial properties in acid-neutral conditions, and also show the influence of different non-specifically adsorbed anions on the interfacial properties that cannot be evidenced only by cyclic voltammetry.

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“…In order to gain further insight into the electrosorbing species responsible for the principal 2D Pt{110} voltammetric peaks recorded for CO-cooled electrodes, CV data were collected in electrolytes containing anions of differing specific adsorption strength at almost constant pH, namely (bi)sulphate, fluoride, methyl sulphonate and perchlorate. Studies with methanesulfonic or trifluoromethanesulfonic acids illustrate the effect of non-adsorbing anions on the structure of interfacial water [41,42]. In addition, the pH dependence of the Hupd region of Pt{110} was investigated using a sodium fluoride buffer [28].…”

Section: Potential Dependence Of Hupd Electrosorption Peaks On Specifmentioning

confidence: 99%

The voltammetry of surfaces vicinal to Pt{110}: Structural complexity simplified by CO cooling

Attard

Hunter

Wright

et al. 2017

Journal of Electroanalytical Chemistry

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By flame-annealing and cooling a series of Pt n{110} × {111} and Pt n{110} × {100} single crystal electrodes in a CO ambient, new insights into the nature of the electrosorption processes associated with Pt{110} voltammetry in aqueous acidic media are elucidated. For Pt n{110} × {111} electrodes, a systematic change in the intensities of so-called hydrogen underpotential (Hupd) and oxide adsorption voltammetric peaks (for two dimensionally ordered (1 × 1) terraces and linear {111} × {111}step sites) point to a lack of surface reconstruction with all surfaces adopting a (1 × 1) configuration. This is in contrast to hydrogen cooled analogues which give rise to significant residual surface disorder, probably associated with the excess 50% of atoms remaining atop of the surface upon deconstruction of the {110} − (1 × 2) terrace phase. In contrast, Pt n{110} × {100} stepped electrodes, when cooled in gaseous CO following flame-annealing, show a marked tendency towards surface reconstruction, even at low step densities. Variations in potential of the Pt{110}-(1 × 1) Hupd electrosorption peaks as a function of specific ion adsorption strength and pH point to weak specific adsorption for both anions (including perchlorate and fluoride) and cations (including Na + and K +). CO charge-displacement measurements of the potential of zero total charge (PZTC) allow inferences to be made concerning the nature of the electrosorbed species in the hydrogen underpotential deposition (Hupd) region. Hence, a coherent interpretation of the complex voltammetric phenomena often displayed by platinum surfaces vicinal to the {110} plane is proposed.

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Interaction of water with methanesulfonic acid on Pt single crystal electrodes

Cited by 13 publications

References 30 publications

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

Study of the Pt (111) | electrolyte interface in the region close to neutral pH solutions by the laser induced temperature jump technique

The voltammetry of surfaces vicinal to Pt{110}: Structural complexity simplified by CO cooling

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