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Electrochemical Growth of Surface Oxides on Nickel. Part 2: Formation of β-Ni(OH)2 and NiO 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 is examined at various polarization potentials (E p), polarization times (t p), and temperatures (T) in the 0.7 ≤ E p ≤ 1.2 V versus RHE, 60 ≤ t p ≤ 10,800 s, and 288 ≤ T ≤ 318 K ranges. The oxide chemical composition is determined using X-ray photoelectron spectroscopy (XPS) and its thickness using XPS depth profiling. XPS measurements demonstrate that such formed oxide layers are multilayer in nature and contain both β-Ni(OH)2 and NiO, with β-Ni(OH)2 being the predominant, outermost species and NiO forming a thin layer sandwiches between metallic Ni and β-Ni(OH)2. An increase of E p, t p, and/or T results in an increase of the oxide thickness. XPS depth profiling measurements reveal that the thickness (d) of the β-Ni(OH)2 plus NiO layers is in the 2 ≤ d ≤ 11 nm range, depending on E p, t p, and T. The electrochemical formation of β-Ni(OH)2 plus NiO follows an inverse-logarithmic growth kinetic law with the escape of metal cation from the metal into the oxide at the inner metal/oxide interface being the rate-determining step. The oxide growth is treated mathematically using the Mott–Cabrera oxide growth theory.

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Acknowledgments

We acknowledge financial support from the NSERC of Canada and Queen’s University, and 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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  2. Michal Grden
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  3. Gregory Jerkiewicz
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Correspondence to Gregory Jerkiewicz.

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Michal Grden is on leave of absence from Warsaw University.

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Alsabet, M., Grden, M. & Jerkiewicz, G. Electrochemical Growth of Surface Oxides on Nickel. Part 2: Formation of β-Ni(OH)2 and NiO in Relation to the Polarization Potential, Polarization Time, and Temperature. Electrocatalysis 5, 136–147 (2014). https://doi.org/10.1007/s12678-013-0172-z

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