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Electrochemical Growth of Surface Oxides on Nickel. Part 1: Formation of α-Ni(OH)2 in Relation to the Polarization Potential, Polarization Time, and Temperature

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Abstract

Electro-oxidation of Ni(poly) in 0.5 M aqueous KOH solution at various polarization potentials (E p) up to 0.5 V vs. reversible hydrogen electrode, for polarization times (t p) up to 2 h, and at 285 ≤ T ≤ 318 K leads to the formation of a thin layer of α-Ni(OH)2. Interfacial capacitance measurements show that the Ni(poly) electrode covered with a layer of α-Ni(OH)2 can be completely reduced back to its metallic state by applying a negative-going potential scan with a lower potential limit of −0.2 V. An increase of E p, t p, and/or T results in an increase of the thickness of the α-Ni(OH)2 layer, which, however, never exceeds two monolayers. The electrochemical formation of α-Ni(OH)2 follows a direct logarithmic growth kinetic law. The results reported in this contribution and their interpretation imply that other oxide growth theories, such as the Langmuir-type adsorption, the point defect model, the electron tunneling, or the nucleation-and-growth model, are not applicable to the growth of α-Ni(OH)2. The potentiostatic growth of α-Ni(OH)2 on Ni(poly) is successfully treated by applying the interfacial place-exchange mechanism and the associated kinetic law.

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Acknowledgments

We acknowledge financial support from the NSERC of Canada and Queen’s University, and on-going collaboration with VALE (formerly Vale-Inco). M. Alsabet thanks Kuwait University for a graduate fellowship. M. Grden acknowledges a leave of absence from Warsaw University.

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  1. Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, ON, K7L 3N6, Canada

    Mohammad Alsabet, Michal Grden & Gregory Jerkiewicz

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  1. Mohammad Alsabet
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Correspondence to Gregory Jerkiewicz.

Appendix

Appendix

In the manuscript, we discuss the dependence of the slope of q ox vs. log t p plots on E p and assign it to the change in the structure of the Ni(OH)2 oxide layer. Here, we justify why this dependence cannot be the result of (a) a variation in the μ value as the electric field changes or (b) a change in the structure of the electrode–electrolyte interface.

With regards to (a), at a first glance, the dependency of the slope of q ox vs. log t p relationships on E p could be the result of a variation in the dipole moment induced by varying the value of E el, which is related to E p. This proposal is examined by the following simple calculations. We assume that the strength of the electric field within the oxide/hydroxide film is of the order of 108 V m–1 for a potential drop of 0.1 V [88, 90] and that the value of NiO polarizability volume (α′) is ca. 4 Å3 [92]. Although we did not found any polarizability data for NiOH, we can assume that its value is similar to that of NiO. Thus, we can apply a simplified formula to estimate the influence of changes in the electric field on the induced dipole moment (μ ind) using Eq. 9

$$ {\mu_{\text{ind}}} = 1.1126 \times {10^{{ - 16}}}\alpha \prime \Delta {E_{\text{el}}} $$
(9)

where ΔE el is the change in electric field, related to the change in the electrode potential. The factor 1.1126 × 10–16 contains the vacuum dielectric permittivity and π [93]. Thus, for a potential difference of 0.1 V, we expect ΔE el to be of the order of 108 V m–1 [88, 90]. After introducing this value into Eq. 9, we obtain a change of the dipole moment of the order of 10–3 D. Assuming that in the case of Ni electro-oxidation the dipole moment calculated using Eq. 3 is of the order of μ = 1.17–1.56 D (see the main body of the manuscript), the value of μ ind is insignificant and cannot explain 6–48% changes in the slope of the q ox vs. log t p relationships.

With regards to (b), in the case of formation of oxide layers on Au and Pt electrodes, Conway et al. [82] suggested, but never proved, that the slope of the q ox vs. log t p relationships could depend on E p in the very initial stages of electro-oxidation. They attributed this effect to simultaneously occurring surface processes, such as anion adsorption. The surface coverage of the electrode with various adsorbed species such as water and/or hydroxyl anions is expected to be potential dependent. Thus, various arrangements of adsorbed species at different potential values could influence the structure of surface oxide/hydroxide layer and result in the potential dependence of the q ox vs. log t p relationships. However, the potential dependent H2O/OH− surface coverage could affect the slope of the q ox vs. log t p plots, thus changing the surface area (A in Eq. 3) available for the formation of Ni(OH)2. On the remaining, uncovered surface, the oxidation would have to follow H2O/OH− adsorption, therefore resulting only in a slightly different slope of the q ox vs. log t p relationships on E p, which is not the case. It is worthwhile adding that the adsorption of K+ cations originating from the electrolyte was considered not to have any significant influence on the Ni electro-oxidation [25].

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Alsabet, M., Grden, M. & Jerkiewicz, G. Electrochemical Growth of Surface Oxides on Nickel. Part 1: Formation of α-Ni(OH)2 in Relation to the Polarization Potential, Polarization Time, and Temperature. Electrocatal 2, 317–330 (2011). https://doi.org/10.1007/s12678-011-0067-9

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