A Carbon Electrode Functionalized by a Tricopper Cluster Complex: Overcoming Overpotential and Production of Hydrogen Peroxide in the Oxygen Reduction Reaction
Dr. Natarajan Thiyagarajan
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Damodar Janmanchi
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Yi-Fang Tsai
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorWondemagegn Hailemichael Wanna
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Ravirala Ramu
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorCorresponding Author
Prof. Dr. Sunney I. Chan
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorCorresponding Author
Prof. Dr. Jyh-Myng Zen
Department of Chemistry, National Chung Hsing University, Taichung City 402, Taiwan) (R.O.C.
Search for more papers by this authorCorresponding Author
Prof. Dr. Steve S.-F. Yu
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Natarajan Thiyagarajan
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Damodar Janmanchi
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Yi-Fang Tsai
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorWondemagegn Hailemichael Wanna
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorDr. Ravirala Ramu
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorCorresponding Author
Prof. Dr. Sunney I. Chan
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorCorresponding Author
Prof. Dr. Jyh-Myng Zen
Department of Chemistry, National Chung Hsing University, Taichung City 402, Taiwan) (R.O.C.
Search for more papers by this authorCorresponding Author
Prof. Dr. Steve S.-F. Yu
Institute of Chemistry, Academia Sinica, Nankang, Taipei, 11529 Taiwan) (R.O.C
Search for more papers by this authorGraphical Abstract
Involvement of a synthetic copper triad in binding and reduction of O2 is demonstrated. The presence of the third Cu ion is crucial to supplying the third reducing equivalent for O−O bond cleavage and reduces the overpotential.
Abstract
A study of the oxygen reduction reaction (ORR) on a screen printed carbon electrode surface mediated by the tricopper cluster complex Cu3(7-N-Etppz(CH2OH)) dispersed on electrochemically reduced carbon black, where 7-N-Etppz(CH2OH) is the ligand 3,3′-(6-(hydroxymethyl)-1,4-diazepane-1,4-diyl)bis(1-(4-ethyl piperazin-1-yl)propan-2-ol), is described. Onset oxygen reduction potentials of about 0.92 V and about 0.77 V are observed at pH 13 and pH 7 vs. the reversible hydrogen electrode, which are comparable to the best values reported for any synthetic copper complex. Based on half-wave potentials (E1/2), the corresponding overpotentials are about 0.42 V and about 0.68 V, respectively. Kinetic studies indicate that the trinuclear copper catalyst can accomplish the 4 e− reduction of O2 efficiently and the ORR is accompanied by the production of only small amounts of H2O2. The involvement of the copper triad in the O2 activation process is also verified.
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