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The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media

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Abstract

The electrochemical formation of α-Ni(OH)2 and NiOOH in the presence of adsorbed oxalate in alkaline media is studied under well-controlled experimental conditions that include the variation of the system temperature (T = −10 to 20 °C), the scan rate (v = 20, 150, and 200 mV s−1), and the concentration of supporting electrolyte (0.10 and 0.50 M KOH). The studies are carried out using cyclic voltammetry (CV) with polycrystalline bulk nickel and nickel foams. In situ infrared spectroscopy with voltammetry confirms the adsorption of oxalate to the surface of nickel in the 0.10 to 0.30 V potential window, concurrent with the formation of the α-Ni(OH)2 species. The presence of oxalate in the system increases the charge density (Q) for the formation of both the α-Ni(OH)2 and NiOOH surface oxides. The Q values calculated under various conditions indicate that the presence of oxalate in the system encourages the formation of a full single monolayer (ML) of NiOOH in the first CV scan. Measurements carried out at room temperature demonstrate that an increase in v decreases the Q values for NiOOH in the presence of oxalate to minimum values achieved at v ≥150 mV s−1. An increase of KOH concentration results in the formation of a thicker layer of NiOOH both in the presence and absence of oxalate. The Q values of NiOOH reduction in conditions that favor the formation of one complete monolayer of NiOOH are used to calculate the specific surface areas of open-cell nickel foams. The calculation of electrochemical surface area using this method is discussed and evaluated with respect to calculations based on the charge of α-Ni(OH)2 formation.

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Acknowledgments

The authors gratefully acknowledge financial support from the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES). A.F.B. Barbosa acknowledges financial support from the CAPES, and J van Drunen acknowledges financial support from the FAPESP (process number 2013/22277-4).

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Authors and Affiliations

  1. Instituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador São Carlense 400 CP 780, São Carlos, SP, CEP 13560-970, Brazil

    Julia van Drunen, Amaury F. B. Barbosa & Germano Tremiliosi-Filho

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  1. Julia van Drunen
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  2. Amaury F. B. Barbosa
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  3. Germano Tremiliosi-Filho
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Correspondence to Julia van Drunen or Germano Tremiliosi-Filho.

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van Drunen, J., Barbosa, A.F.B. & Tremiliosi-Filho, G. The Formation of Surface Oxides on Nickel in Oxalate-Containing Alkaline Media. Electrocatalysis 6, 481–491 (2015). https://doi.org/10.1007/s12678-015-0268-8

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