Understanding electrochemical interfaces through comparing experimental and computational charge density–potential curves

Mohandas, Nandita; Bawari, Sumit; Shibuya, Jani J. T.; Ghosh, Soumya; Mondal, Jagannath; Narayanan, Tharangattu N.; Cuesta, Angel

doi:10.1039/d4sc00746h

Cited by 4 publications

References 108 publications

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Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide

Yukuhiro,

Vicente,

Fernández

et al. 2024

J. Am. Chem. Soc.

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The activity of Pt for the electro-oxidation of several organic molecules changes with the cation of the electrolyte. It has been proposed that the underlying reason behind that effect is the so-called noncovalent interactions between the hydrated cations and adsorbed OH (OH ad ). However, there is a lack of spectroscopic evidence for this phenomenon, resulting in an incomplete understanding at the microscopic level of these electrochemical processes. Herein, we explore the electro-oxidation of glycerol (EOG) on platinum (Pt) in LiOH, NaOH and KOH using in situ surface-enhanced infrared absorption spectroscopy in the attenuated total reflectance mode (ATR-SEIRAS) and in situ X-ray absorption spectroscopy (XAS). Our results show that the electrolyte cation influences the rate and potential at which adsorbed CO (CO ad ), a catalytic poison, is formed and oxidized. We attribute this to the cation-dependent stability of oxygenated species on the metallic Pt surface and the different intensities of the electric field at the electrode/electrolyte interface. We also demonstrate that the formation of an inactive Pt oxide layer is indirectly also cationdependent: the formation of this layer is triggered by the cation-dependent oxidative removal of reaction intermediates (for instance, CO). This phenomenon explains the well-known cation-induced differences in the voltammetric profiles, of not just glycerol, but generally of alcohols and polyols.

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Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide

Yukuhiro,

Vicente,

Fernández

et al. 2024

J. Am. Chem. Soc.

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Water at electrode–electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations

Gunasekaran,

Du,

Burley

et al. 2024

Chem. Sci.

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Water at electrode-electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations

Cuesta,

Gunasekaran,

et al. 2024

Preprint

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We have undertaken a vibrational study of the structure of interfacial water and its potential dependence using H2O:D2O mixtures to explore the O-H and O-D stretching modes of HOD as well as the bending modes of HOD and H2O. Due to the symmetry reduction, some of the complexity characteristic of the vibrational spectrum of water is removed in HOD. Coupled with potential-dependent ab-initio simulations of the gold-water interface, this has enabled a deeper insight into the hydrogen-bond network of interfacial water and into how it is affected by the applied potential. Possibly the most important conclusions of our work are (i) the absence of any ice-like first layer of interfacial water at any potential and (ii) that interfacial water reorients around a stable backbone of hydrogen bonds roughly parallel to the electrode surface. At E > pzc, interfacial water molecules are oriented with the oxygen lone pairs towards the surface and forming exclusively or nearly exclusively hydrogen-donating hydrogen bonds with other water molecules. At E < pzc, the oxygen lone pairs point away from the surface instead, but the population of hydrogen-donating water molecules does not vanish. In fact, the population of hydrogen-accepting water molecules only dominates at considerably negative charge densities, due to the weak interaction of the hydrogen atoms of interfacial water molecules with the Au surface.

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Understanding electrochemical interfaces through comparing experimental and computational charge density–potential curves

Abstract: Electrode-electrolyte interfaces play a decisive role in electrochemical charge accumulation and transfer processes. Theoretical modelling of these interfaces is critical to decipher the microscopic details of such phenomena. Different force...

Cited by 4 publications

References 108 publications

Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide

Alkaline-Metal Cations Affect Pt Deactivation for the Electrooxidation of Small Organic Molecules by Affecting the Formation of Inactive Pt Oxide

Water at electrode–electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations

Water at electrode-electrolyte interfaces: combining HOD vibrational spectra with ab initio-molecular dynamics simulations

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