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Molecular electrocatalysts for the oxygen reduction reaction

Abstract

The past decade has seen considerable growth in the development of materials for fuel cell electrodes, and there is a desire for active electrocatalysts derived from base metals instead of noble metals. Fuels cells that consume H2 and O2 require catalysts to cleave these reactants, with the oxygen reduction reaction (ORR) — either 4H+/4e reduction to 2H2O or 2H+/2e reduction to H2O2 — being particularly challenging. The ORR is efficiently performed by certain metalloenzymes, and understanding the links between their structure and function aids the design of molecular ORR electrocatalysts. These bio-inspired catalysts exhibit good activity relative to previous synthetic systems and, furthermore, have provided mechanistic insights relevant to synthetic and enzymatic catalysts. This Review covers recent developments in homogeneous and heterogeneous molecular ORR catalysis, placing emphasis on reaction mechanisms and the factors governing rates and selectivities.

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Figure 1: Dioxygen (O2) is processed in nature by metalloenzymes.
Figure 2: Homogeneous ORR electrocatalysts featuring first-row transition metals.
Figure 3: Transforming molecular catalysts into heterogeneous ORR electrocatalysts by immobilization on electrode surfaces.
Figure 4: Heterogeneous ORR catalysts prepared from synthetic metalloporphyrins, which are amenable to spectroscopic analysis for mechanistic study.
Figure 5: An enzyme model and catalytic cycles proposed for mononuclear and dinuclear metalloporphyrin catalysts.
Figure 6: A selection of metallocorroles that have been investigated as ORR catalysts.
Figure 7: Metallophthalocyanines recently investigated as catalysts for the electrocatalytic ORR.
Figure 8: Synthetic aporphynoid copper complexes investigated as catalysts for the ORR.
Figure 9: Synthetic high-valent and low-valent diiron catalysts for the ORR.

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Acknowledgements

The authors acknowledge their research grant from the India Department of Science and Technology, Science and Engineering Research Board (SERB) EMR/2014/000392.

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S.D., B.M., S.C. and A.D. researched the references and wrote the manuscript. A.R. and S.A. assisted in the presentation of the text and images. All authors contributed to discussions. S.D., B.M. and A.D. performed editing and corrections. S.D. and A.D revised the manuscript before the final submission.

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Dey, S., Mondal, B., Chatterjee, S. et al. Molecular electrocatalysts for the oxygen reduction reaction. Nat Rev Chem 1, 0098 (2017). https://doi.org/10.1038/s41570-017-0098

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