TY - JOUR
T1 - Nonprecious metal catalysts for fuel cell applications
T2 - electrochemical dioxygen activation by a series of first row transition metal tris(2-pyridylmethyl)amine complexes
AU - Ward, Ashleigh L.
AU - Elbaz, Lior
AU - Kerr, John B.
AU - Arnold, John
N1 - © 2012 American Chemical Society
PY - 2012/4/16
Y1 - 2012/4/16
N2 - A series of divalent first row triflate complexes supported by the ligand tris(2-pyridylmethyl)amine (TPA) have been investigated as oxygen reduction catalysts for fuel cell applications. [(TPA)M 2+] n+ (M = Mn, Fe, Co, Ni, and Cu) derivatives were synthesized and characterized by X-ray crystallography, cyclic voltammetry, NMR spectroscopy, magnetic susceptibility, IR spectroscopy, and conductance measurements. The stoichiometric and electrochemical O 2 reactivities of the series were examined. Rotating-ring disk electrode (RRDE) voltammetry was used to examine the catalytic activity of the complexes on a carbon support in acidic media, emulating fuel cell performance. The iron complex displayed a selectivity of 89% for four-electron conversion and demonstrated the fastest reaction kinetics, as determined by a kinetic current of 7.6 mA. Additionally, the Mn, Co, and Cu complexes all showed selective four-electron oxygen reduction (<28% H 2O 2) at onset potentials (∼0.44 V vs RHE) comparable to state of the art molecular catalysts, while being straightforward to access synthetically and derived from nonprecious metals.
AB - A series of divalent first row triflate complexes supported by the ligand tris(2-pyridylmethyl)amine (TPA) have been investigated as oxygen reduction catalysts for fuel cell applications. [(TPA)M 2+] n+ (M = Mn, Fe, Co, Ni, and Cu) derivatives were synthesized and characterized by X-ray crystallography, cyclic voltammetry, NMR spectroscopy, magnetic susceptibility, IR spectroscopy, and conductance measurements. The stoichiometric and electrochemical O 2 reactivities of the series were examined. Rotating-ring disk electrode (RRDE) voltammetry was used to examine the catalytic activity of the complexes on a carbon support in acidic media, emulating fuel cell performance. The iron complex displayed a selectivity of 89% for four-electron conversion and demonstrated the fastest reaction kinetics, as determined by a kinetic current of 7.6 mA. Additionally, the Mn, Co, and Cu complexes all showed selective four-electron oxygen reduction (<28% H 2O 2) at onset potentials (∼0.44 V vs RHE) comparable to state of the art molecular catalysts, while being straightforward to access synthetically and derived from nonprecious metals.
UR - http://www.scopus.com/inward/record.url?scp=84859799199&partnerID=8YFLogxK
U2 - 10.1021/ic2026957
DO - 10.1021/ic2026957
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C2 - 22458367
SN - 0020-1669
VL - 51
SP - 4694
EP - 4706
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 8
ER -