Journal
INORGANIC CHEMISTRY
Volume 52, Issue 24, Pages 14317-14325Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic402297f
Keywords
-
Categories
Funding
- Department of Science and Technology, India [DST/SR/IC-35-2009]
- Council of Scientific and Industrial Research (CSIR), India [01(2412)10/EMr-II]
- CSIR-SRF fellowship
- IACS
Ask authors/readers for more resources
An iron porphyrin catalyst bearing four ferrocenes and a hydrogen bonding distal pocket is found to catalyze 4e(-)/4H(+) oxygen reduction reaction (ORR) in organic solvent under homogeneous conditions in the presence of 2-3 equiv of Trifluoromethanesulphonic acid. Absorption spectroscopy, electron paramagnetic resonance (EPR), and resonance Raman data along with H2O2 assay indicate that one out of the four electrons necessary to reduce O-2 to H2O is donated by the ferrous porphyrin while three are donated by the distal ferrocene residues. The same catalyst shows 4e(-)/4H(+) reduction of O-2 in an aqueous medium, under heterogeneous conditions, over a wide range of pH. Both the selectivity and the rate of ORR are found to be pH independent in an aqueous medium. The ORR proceeds via a proton transfer followed by electron transfer (PET) step in an organic medium and while a 2e(-)/1H(+) proton coupled electron transfer (PCET) step determines the electrochemical potential of ORR in an aqueous medium.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available