Change of mechanism of the hydrogen-electrode reaction with overpotential—I. distribution of the reaction affinity among constituent steps

Enyo, M.

doi:10.1016/0013-4686(73)80005-2

Cited by 33 publications

(9 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…There are two situations for this route: when j 0T < j 0V (in acidic solution), η T ≈ η at low overpotential and this corresponds to the Tafel-Horiuti mechanism, the fugacity of H in Pd can be expressed by the Nernst relation, x increases with the cathodic cd; when j 0T << j 0V (in basic solution and at high pressure), η T = 0 and the her follows the V-T mechanism at low overpotential, the fugacity remains at the equilibrium value, as well as x. At high overpotential, the her follows the linked V-T mechanism for both situations and η T /η approaches 2(1-β V )/(3-β V ) as predicted by Enyo as early as 1973 [20]. …”

Section: V-t Routementioning

confidence: 73%

The maximum hydrogen (deuterium) loading ratio in the Pd|H2O (D2O) electrochemical system

Zhang

1997

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

Based on the Volmer-Heyrovsky-Tafel mechanism, Frumkin adsorption and thermodynamic data of hydrogen (deuterium) absorption in Pd, effects of surface parameters on the hydrogen (deuterium) loading ratio into Pd in the hydrogen (deuterium) evolution reaction are discussed. There is a change of mechanism from the Volmer-Tafel route to the Volmer-Heyrovsky route when the current density rises, and there exists the maximum loading ratio at a certain current density when the symmetry factor of the Heyrovsky step is less than that of the Volmer reaction. The theoretical results fit the experimental data presented before very well; other factors that affect the loading ratio are discussed as well.

show abstract

Section: V-t Routementioning

confidence: 73%

The maximum hydrogen (deuterium) loading ratio in the Pd|H2O (D2O) electrochemical system

Zhang

1997

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

show abstract

“…This is because a RDS should fulfill the following two requirements: (1) an RDS is a step to control the overall reaction rate; and (2) all other steps have to be rapid so that these steps can be regarded as being in quasi-equilibrium during irreversible electrode processes. This issue was pointed out and intensively discussed by Enyo in the 1970s. − As Wang and co-workers also mentioned, these results illustrate that the traditional simple analytical approach could mislead conclusions if the corresponding electrode processes transform their RDS as a function of potential or there is no RDS in processes.…”

Section: Resultsmentioning

confidence: 93%

Fast-Decoding Algorithm for Electrode Processes at Electrified Interfaces by Mean-Field Kinetic Model and Bayesian Data Assimilation: An Active-Data-Mining Approach for the Efficient Search and Discovery of Electrocatalysts

Sakaushi

Watanabe

Kumeda

et al. 2022

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

The microscopic origins of the activity and selectivity of electrocatalysts has been a long-lasting enigma since the 19th century. By applying an active-data-mining approach, employing a mean-field kinetic model and a statistical approach of Bayesian data assimilation, we demonstrate here a fast decoding to extract key properties in the kinetics of complicated electrode processes from current–potential profiles in experimental and literary data. As the proof-of-concept, kinetic parameters on the four-electron oxygen reduction reaction in the 0.1 M HClO4 solution (ORR: O2 + 4e – + 4H+ → 2H2O) of various platinum-based single-crystal electrocatalysts are extracted from our own experiments and third-party literature to investigate the microscopic electrode processes. Furthermore, data assimilation of the mean-field ORR model and experimental data is performed based on Bayesian inference for the inductive estimation of kinetic parameters, which sheds light on the dynamic behavior of kinetic parameters with respect to overpotential. This work shows that a fast-decoding algorithm based on a mean-field kinetic model and Bayesian data assimilation is a promising data-driven approach to extract key microscopic features of complicated electrode processes and therefore will be an important method toward building up advanced human–machine collaborations for the efficient search and discovery of high-performance electrochemical materials.

show abstract

“…Minor modifications are necessary in applying the preceding analysis to electrode processes (anodic in the forward direction) (sufficient to complete the changeover of the RDS) would require a rather short range, some 0.18 volt at room temperature [12]. Such a changeover of the RDS was actually found [5] to take place within the potential range of about 0.2 volt.…”

Section: Application To Electrode Processesmentioning

confidence: 97%

Shift of the rate‐determining step in a consecutive chemical reaction with variation of the reaction affinity

Enyo

1975

Int J of Chemical Kinetics

Self Cite

View full text Add to dashboard Cite

show abstract

Change of mechanism of the hydrogen-electrode reaction with overpotential—I. distribution of the reaction affinity among constituent steps

Cited by 33 publications

References 8 publications

The maximum hydrogen (deuterium) loading ratio in the Pd|H2O (D2O) electrochemical system

The maximum hydrogen (deuterium) loading ratio in the Pd|H2O (D2O) electrochemical system

Fast-Decoding Algorithm for Electrode Processes at Electrified Interfaces by Mean-Field Kinetic Model and Bayesian Data Assimilation: An Active-Data-Mining Approach for the Efficient Search and Discovery of Electrocatalysts

Shift of the rate‐determining step in a consecutive chemical reaction with variation of the reaction affinity

Contact Info

Product

Resources

About