Oxygen reduction reaction (ORR) is important in artificial energy conversion systems such as fuel cells. However, it is kinetically sluggish. It is thereby highly desirable to develop ORR catalysts to improve the efficiency of energy conversion. In this work, three copper(II) complexes based on the hexadentate tetrapyridylalkylamine N,N,N’,N’-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn), namely [Cu2(tpbn)(CH3OH)4(ClO4)2](ClO4)2 (Cu-tpbn), [Cu2(tpbn)(bpy)2](ClO4)4.2CH3COCH3 (Cu-tpbn-bpy, bpy = 2,2′-bipyridine), and [Cu2(tpbn)(Me2bpy)2](ClO4)4.3CH3CN (Cu-tpbn-Me2bpy, Me2bpy = 4,4′-dimethyl-2,2′-bipyridine), were prepared and their catalytic properties for ORR studied. All three complexes were homogeneous electrocatalysts for ORR in neutral phosphate buffer solutions. The ORR mediated by Cu-tpbn-Me2bpy had the most positive onset potential of 0.461 V vs RHE. In the applied potential window of -0.19 – 0.50 V vs RHE, Cu-tpbn boosted the stepwise four-electron ORR to mainly produce H2O, whereas Cu-tpbn-bpy and Cu-tpbn-Me2bpy mediated the ORR to mainly generate H2O2. The rate constants for the ORR to H2O promoted by Cu-tpbn, Cu-tpbn-bpy and Cu-tpbn-Me2bpy were 1.2 × 103 s−1, 3.2 × 10 s−1 and 7.8 × 10 s−1, respectively. The foot-of-the-wave analysis showed that the turnover frequencies for the reduction of O2 to H2O2 mediated by Cu-tpbn, Cu-tpbn-bpy and Cu-tpbn-Me2bpy were 1.5 × 104 s−1, 7.5 × 10 s−1 and 2.7 × 102 s−1, respectively. Meanwhile, complexes Cu-tpbn-bpy and Cu-tpbn-Me2bpy were more stable than Cu-tpbn. This work unveiled that the catalytic activity and the product selectivity of the ORR were greatly associated with the denticity, the steric effect and the electronic property of the organic ligands.
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