Geometrically asymmetric electrodes for probing electrochemical reaction kinetics: a case study of hydrogen at the Pt–CsH2PO4 interface

文献情報

出版日 2009-07-15
DOI 10.1039/B909498A
インパクトファクター 3.676
著者

Kenji A. Sasaki, Yong Hao, Sossina M. Haile


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要旨

Electrochemical reactions can exhibit considerable asymmetry, with the polarization behavior of oxidation at a given metal|electrolyte interface differing substantially from that of reduction. The reference-less, microcontact electrode geometry, in which the electrode overpotentials are geometrically constrained to the working electrode (by limiting its area) is experimentally convenient, particularly for fuel cell studies, because the results do not rely on accurate placement of a reference electrode nor must oxidant and reductant gases be sealed off from one another. Here, the conditions under which the critical assumption of this geometry applies—that the overpotential at the large-area counter electrode can be ignored—is numerically assessed. It is found that, for cells of sufficiently large area, the effective radius of the counter electrode (which defines the area through which the majority of the current passes) can be expressed directly as a function of electrolyte thickness and the materials properties, σ, the conductivity of the electrolyte, and k, the reaction rate constant for the electrochemical reaction at zero-bias. From this effective radius and the true radius of the working electrode, the fraction of electrode overpotential at the latter, defined as the extent of isolation, can be readily computed. Experimental studies of hydrogen electro-oxidation/proton electro-reduction at the Pt|CsH2PO4 interface using two cells of differing dimensions both validate the computational results and demonstrate that asymmetry in such reactions are readily revealed in the micro-electrode, reference-less geometry. The study furthermore confirms the insensitivity of the results to the precise placement of the working electrode, while indicating the importance of very high isolation values (>99%) to ensure that overpotential contributions of the counter electrode do not influence the measurements, particularly as bias is increased.

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Physical Chemistry Chemical Physics
CiteScore: 5.5
自己引用率: 10.3%
年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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