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Mechanisms of Two-Electron versus Four-Electron Reduction of Dioxygen Catalyzed by Earth-Abundant Metal Complexes

Title
Mechanisms of Two-Electron versus Four-Electron Reduction of Dioxygen Catalyzed by Earth-Abundant Metal Complexes
Authors
Fukuzumi, ShunichiLee, Yong-MinNam, Wonwoo
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2018
Journal Title
CHEMCATCHEM
ISSN
1867-3880JCR Link1867-3899JCR Link
Citation
vol. 10, no. 1, pp. 9 - 28
Keywords
reaction mechanismsearth-abundant metalsoxygen reduction reactionProton-Coupled Electron Transfer
Publisher
WILEY-V C H VERLAG GMBH
Indexed
SCIE; SCOPUS WOS scopus
Abstract
The two-electron reduction of dioxygen with two protons produces hydrogen peroxide, which is directly used as a liquid fuel in hydrogen peroxide fuel cells, whereas the four-electron reduction of dioxygen is combined with the two-electron oxidation of hydrogen in hydrogen fuel cells. Platinum (Pt)-based nanocomposites are the most efficient commercial electrocatalysts for the oxygen reduction reaction (ORR). However, the poor stability, scarcity and high cost of these Pt-based oxygen electrocatalysts are major barriers for the large-scale implementation of fuel cell technologies. Replacing noble metal-based electrocatalysts with highly efficient and inexpensive earth-abundant metal-based oxygen electrocatalysts has been of critical importance for practical applications. To develop efficient catalysts for the two-electron and four-electron reduction of dioxygen, it is crucially important to clarify the catalytic mechanisms of two-electron/two-proton versus four-electron/four-proton reduction of dioxygen with earth-abundant metal complexes. This review focused on the factors that control the two-electron/two-proton versus four-electron/four-proton reduction of dioxygen by electron donors (one electron reductants) such as ferrocene, catalyzed by earth-abundant metal complexes such as iron, cobalt, copper, manganese and nickel complexes in the homogeneous phase, by detecting catalytic intermediates, which determine the catalytic pathways of the two-electron versus four-electron reduction of dioxygen. The electrocatalytic two-electron or/and four-electron reduction of dioxygen with earth-abundant metal complexes and metal oxides has also been discussed in relation with the homogeneous catalysis.
DOI
10.1002/cctc.201701064
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
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