2017
DOI: 10.1149/2.0191711jes
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Electrochemical Hydrogen Evolution: H+or H2O Reduction? A Rotating Disk Electrode Study

Abstract: We study the effect of H + and OH − diffusion on the hydrogen evolution reaction in unbuffered aqueous electrolyte solutions of mildly acidic pH values. We demonstrate that the cathodic polarization curves measured on a Ni rotating disk electrode in these solutions can be modeled by assuming two irreversible reactions, the reduction of H + and that of water molecules, both following Erdey-Grúz-Volmer-Butler kinetics. The reduction of H + yields a transport-limited and thus, rotation rate-dependent current at n… Show more

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Cited by 57 publications
(59 citation statements)
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“…1 = 2 H 2 + OH À ) leads apart from H 2 evolution to the formation of an alkaline environment [47,[64][65] with highly active and mobile OHspecimen. [66] pH measured for the electrolyte extracted from the negative electrode was in fact alkaline (ranging from 9.8 to 11.4, interestingly, the pH measured depended on the final voltage, not the procedure), while for positive electrode almost no change was observed (ca. 5.2 vs. 5.9 for initial solution).…”
Section: Resultsmentioning
confidence: 94%
See 1 more Smart Citation
“…1 = 2 H 2 + OH À ) leads apart from H 2 evolution to the formation of an alkaline environment [47,[64][65] with highly active and mobile OHspecimen. [66] pH measured for the electrolyte extracted from the negative electrode was in fact alkaline (ranging from 9.8 to 11.4, interestingly, the pH measured depended on the final voltage, not the procedure), while for positive electrode almost no change was observed (ca. 5.2 vs. 5.9 for initial solution).…”
Section: Resultsmentioning
confidence: 94%
“…Nonetheless, electrolyte reduction (occurring after exceeding the hydrogen storage capacity) at the negative electrode (e.g. H 2 O+e − →1/2 H 2 +OH − ) leads apart from H 2 evolution to the formation of an alkaline environment, with highly active and mobile OH ‐ specimen . pH measured for the electrolyte extracted from the negative electrode was in fact alkaline (ranging from 9.8 to 11.4, interestingly, the pH measured depended on the final voltage, not the procedure), while for positive electrode almost no change was observed (ca.…”
Section: Resultsmentioning
confidence: 99%
“…When considering the pH s change, both the kinetics at the electrochemical interface and the diffusion process must be taken into account. As an example, Grozovski et al developed a diffusion layer model that is divided into two regimes for the numerical simulation of the HER on a Ni electrode (Grozovski et al, 2017). These regimes are separated by a reaction plane over which the local concentrations of H + and OH − (C OH s ) generated by direct H 2 O reduction are balanced.…”
Section: Ordinary Differential Equation Modelingmentioning
confidence: 99%
“…The selfionization of H 2 O is neglected, due to that using documented rate constants of ionization/neutralization will result in severe deviation of current curves in the pH range from 2.5 to 4 ( Figure S3), which may be attributed to the unusual dynamics of H + /OHwithin the electrical double layer. 28,29 As shown in Figure 2a, the calculated polarization curves are divided into the acidic and alkaline current branches. In the HER region, the acidic and alkaline mechanism regions are isolated by the plateau in each curve, characterizing the H + diffusion-control kinetics.…”
mentioning
confidence: 99%