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Inorg Chem. 2012 Apr 2;51(7):3932-4. doi: 10.1021/ic3001619. Epub 2012 Mar 21.

Homogeneous CO2 reduction by Ni(cyclam) at a glassy carbon electrode.

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Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093-0358, United States.


The homogeneous CO(2) reduction activity of several nickel cyclam complexes was examined by cyclic voltammetry and controlled potential electrolysis. CO production with high efficiency from unsubstituted Ni(cyclam) was verified, while the activity was found to be attenuated with methyl substitution of the amines on the cyclam ring. Reactivity with CO(2) was also probed using density functional theory (DFT) calculations. The relative CO(2) binding energies to the Ni(I) state obtained from DFT were found to match well with the experimental results and shed light on the possible importance of the isomeric form of Ni(cyclam) in determining the catalytic activity.


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