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Electrochemistry of nickel(II) and copper(II) N,N′-ethylenebis(acetylacetoniminato) complexes and their electrocatalytic activity for reduction of carbon dioxide and carboxylic acid protons

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Abstract

The effect of the metal center of [ML] complexes [M = Ni(II), Cu(II); L = N,N′-ethylenebis(acetylacetoniminato)] on their electrochemistry and electrocatalytic activity for the reduction of CO2 and protons has been studied using cyclic voltammetry and bulk electrolysis. The two complexes exhibit different electrochemistries, which are not significantly dependent on the nature of the solvent. The electrocatalytic activity of [NiL] is significantly higher than that of [CuL] for CO2 reduction, due to the higher stability of the electrochemically generated [Ni(I)L] complex, relative to the Cu(I) analog. The diffusion coefficient of [NiL] calculated from the steady-state diffusion limiting current is 3.0 × 10−6 cm2 s−1. The catalytic efficiency of [NiL] in non-aqueous solvents in terms of i p(CO2)/i p(N2) per nickel center is smaller than that of [Ni(cyclam)]2+, but greater than those of sterically hindered mononuclear [Ni(1,3,6,8,10, 13,15-heptaazatricyclo(11.3.1.1) octadecane)]2+ or multinuclear [Ni3 (X)]6+ where X = 8,8′,8″-{2,2′,2″(-nitrilotriethyl)-tris(1,3,6,8,10,13,15-heptaazatricyclo(11.3.1.1) octadecane}. Both [NiL] and [CuL] are also electrocatalysts for the reduction of carboxylic acid protons, with the catalytic pathway being different for acetic and trifluoroacetic acids in MeCN.

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Acknowledgments

The authors gratefully acknowledge financial assistance from NSF of Sri Lanka through the research grant (RG/2006/FR/02), the Australian Research Council and an Endeavour Award-2011 Fellowship by DEEWR and AusAid of Australia to Dr. (Mrs.) M.Y.Udugala-Ganehenege. The authors extend their thanks to Prof. J. F. Endicott of Wayne State University, Detroit, MI 48202, USA, for reviewing the paper before submission.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, University of Peradeniya, Peradeniya, Sri Lanka

    Manawadevi Y. Udugala-Ganehenege

  2. Post-Graduate Institute of Science, University of Peradeniya, Peradeniya, Sri Lanka

    Manawadevi Y. Udugala-Ganehenege & N. M. Dissanayake

  3. School of Chemistry, Monash University, Clayton, VIC, 3800, Australia

    Yuping Liu, Alan M. Bond & Jie Zhang

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  1. Manawadevi Y. Udugala-Ganehenege
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  2. N. M. Dissanayake
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Correspondence to Manawadevi Y. Udugala-Ganehenege.

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Udugala-Ganehenege, M.Y., Dissanayake, N.M., Liu, Y. et al. Electrochemistry of nickel(II) and copper(II) N,N′-ethylenebis(acetylacetoniminato) complexes and their electrocatalytic activity for reduction of carbon dioxide and carboxylic acid protons. Transition Met Chem 39, 819–830 (2014). https://doi.org/10.1007/s11243-014-9864-3

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  • DOI: https://doi.org/10.1007/s11243-014-9864-3

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