Sodalite-type Cu-based Three-dimensional Metal-Organic Framework for Efficient Oxygen Reduction Reaction.
Prabu ManiSharat DevadasTamilselvi GurusamyPitchiah Esakki KarthikBalu P RatheeshKothandaraman RamanujamSukhendu MandalPublished in: Chemistry, an Asian journal (2019)
Inspired by copper-based oxygen reduction biocatalysts, we have studied the electrocatalytic behavior of a Cu-based MOF (Cu-BTT) for oxygen reduction reaction (ORR) in alkaline medium. This catalyst reduces the oxygen at the onset (Eonset ) and half-wave potential (E1/2 ) of 0. 940 V and 0.778 V, respectively. The high halfway potential supports the good activity of Cu-BTT MOF. The high ORR catalytic activity can be interpreted by the presence of nitrogen-rich ligand (tetrazole) and the generation of nascent copper(I) during the reaction. In addition to the excellent activity, Cu-BTT MOF showed exceptional stability too, which was confirmed through chronoamperometry study, where current was unchanged up to 12 h. Further, the 4-electrons transfer of ORR kinetics was confirmed by hydrodynamic voltammetry. The oxygen active center namely copper(I) generation during ORR has been understood by the reduction peak in cyclic voltammetry as well in the XPS analysis.