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Redox-active ligand assisted electrocatalytic water oxidation by a mononuclear cobalt complex.

Dalton transactions (Cambridge, England : 2003) (2020-05-16)
Sachidulal Biswas, Suranjana Bose, Joyashish Debgupta, Purak Das, Achintesh N Biswas
ABSTRACT

In this report, the synthesis, characterization and electrocatalytic oxidation of water by a mononuclear cobalt(iii) complex, [CoIII(dpaq)(Cl)]Cl (1) featuring a redox-active pentadentate amidate ligand (H-dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate) is reported. Complex 1 has been found to be a stable and homogeneous water oxidation catalyst (WOC) in 0.1 M phosphate buffer (pH 8.0). A series of experiments (rinse test, SEM, EDX spectroscopy) confirm that this complex acts as a molecular electrocatalyst, and not a precursor of CoOx. The electrocatalytic water oxidation proceeds with high faradaic efficiency (81%) and fast rate (85 s-1). Analysis of the electrochemical reaction kinetics by foot-of-the-wave (FOWA) methodology reveals a high turnover frequency of 1.6 × 104 s-1 which is comparable to the best performing Ru-based WOCs.

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Sigma-Aldrich
Nitric oxide, 98.5%