NDLI: Electrochemical Growth of Surface Oxides on Nickel. Part 3: Formation of β-NiOOH in Relation to the Polarization Potential, Polarization Time, and Temperature

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Electrochemical Growth of Surface Oxides on Nickel. Part 3: Formation of β-NiOOH in Relation to the Polarization Potential, Polarization Time, and Temperature

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Electrochemical Growth of Surface Oxides on Nickel. Part 3: Formation of β-NiOOH in Relation to the Polarization Potential, Polarization Time, and Temperature

Content Provider	Springer Nature Link
Author	Alsabet, Mohammad Grdeń, Michal Jerkiewicz, Gregory
Copyright Year	2014
Abstract	Electro-oxidation of surface β-Ni(OH)$_{2}$ residing on metallic Ni to β-NiOOH was studied in 0.5 M aqueous KOH at 277 K ≤ T ≤ 318 K by means of cyclic voltammetry (CV) and chrono-amperometry (CA). The process is accompanied by a diffusion of H$^{+}$ within the surface oxide phase. The formation of β-NiOOH gives rise to an anodic peak in CV profiles, the potential of which depends on the scan rate (s). An analysis of the relation between the anodic peak current density (j $_{peak, AN}$) and s indicates that the growth of β-NiOOH is controlled by the diffusion of H$^{+}$ and its modelling leads to the determination of the diffusion coefficient of H$^{+}$ (D(H$^{+}$)). In the case of 277 K ≤ T ≤ 318 K, the values of D(H$^{+}$) are of the order of 10$^{–11}$ cm$^{2}$ s$^{–1}$, when calculated with respect to the electrode’s geometric surface area (A $_{geom}$), and of the order of 10$^{–12}$ cm$^{2}$ s$^{–1}$, when calculated with respect to the electrochemically active surface area (A $_{ecsa}$). The activation Gibbs energy of H$^{+}$ diffusion (Δ$_{diff}$ G $^{≠}$(H$^{+}$)) is in the 19.5–22.6 kJ mol$^{–1}$ range. Chrono-amperometry transients for the formation of β-NiOOH are analyzed on the basis of finite-space diffusion, with the assumption that β-NiOOH can be formed through three mechanistic pathways. The values of D(H$^{+}$) determined for both A $_{geom}$ and A $_{ecsa}$ using this approach are of the order of 10$^{–12}$ cm$^{2}$ s$^{–1}$. They are smaller than the analogous values of D(H$^{+}$) determined on the basis of CV measurements but the values of Δ$_{diff}$ G $^{≠}$(H$^{+}$) obtained using these two experimental approaches are comparable.
Starting Page	60
Ending Page	71
Page Count	12
File Format	PDF
ISSN	18682529
Journal	Electrocatalysis
Volume Number	6
Issue Number	1
e-ISSN	18685994
Language	English
Publisher	Springer US
Publisher Date	2014-07-20
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Nickel Electro-oxidation Beta nickel hydroxide Beta nickel oxyhydroxide Proton diffusion mechanism Exponential oxide growth Electrochemistry Physical Chemistry Catalysis Energy Technology
Content Type	Text
Resource Type	Article
Subject	Electrochemistry

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Electrochemical Growth of Surface Oxides on Nickel. Part 3: Formation of β-NiOOH in Relation to the Polarization Potential, Polarization Time, and Temperature