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Title: Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts

Abstract

The oxygen reduction reaction (ORR) is a key component of biological processes and energy technologies. This review provides a comprehensive report of soluble molecular catalysts and electrocatalysts for the ORR. The precise synthetic control and relative ease of mechanistic study for homogeneous molecular catalysts, as compared to heterogeneous materials or surface-adsorbed species, enables a detailed understanding of the individual steps of ORR catalysis. Thus, the review places particular emphasis on ORR mechanism and thermodynamics. First, the thermochemistry of oxygen reduction and the factors influencing ORR efficiency are described to contextualize the discussion of catalytic studies that follows. Reports of ORR catalysis are presented in terms of their mechanism, with separate sections for catalysis proceeding via initial outer- and inner-sphere electron transfer to O2. The rates and selectivities (for production of H2O2 vs H2O) of these catalysts are provided, along with suggested methods for accurately comparing catalysts of different metals and ligand scaffolds that were examined under different experimental conditions.

Authors:
 [1];  [2];  [2];  [2]
  1. YALE UNIVERSITY
  2. Yale University
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1595762
Report Number(s):
PNNL-SA-131661
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Chemical Reviews
Additional Journal Information:
Journal Volume: 118; Journal Issue: 5
Country of Publication:
United States
Language:
English
Subject:
oxygen, electrocatalysis, molecular

Citation Formats

Pegis, Michael L., Wise, Catherine F., Martin, Daniel J., and Mayer, James M. Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts. United States: N. p., 2018. Web. doi:10.1021/acs.chemrev.7b00542.
Pegis, Michael L., Wise, Catherine F., Martin, Daniel J., & Mayer, James M. Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts. United States. doi:10.1021/acs.chemrev.7b00542.
Pegis, Michael L., Wise, Catherine F., Martin, Daniel J., and Mayer, James M. Wed . "Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts". United States. doi:10.1021/acs.chemrev.7b00542.
@article{osti_1595762,
title = {Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts},
author = {Pegis, Michael L. and Wise, Catherine F. and Martin, Daniel J. and Mayer, James M.},
abstractNote = {The oxygen reduction reaction (ORR) is a key component of biological processes and energy technologies. This review provides a comprehensive report of soluble molecular catalysts and electrocatalysts for the ORR. The precise synthetic control and relative ease of mechanistic study for homogeneous molecular catalysts, as compared to heterogeneous materials or surface-adsorbed species, enables a detailed understanding of the individual steps of ORR catalysis. Thus, the review places particular emphasis on ORR mechanism and thermodynamics. First, the thermochemistry of oxygen reduction and the factors influencing ORR efficiency are described to contextualize the discussion of catalytic studies that follows. Reports of ORR catalysis are presented in terms of their mechanism, with separate sections for catalysis proceeding via initial outer- and inner-sphere electron transfer to O2. The rates and selectivities (for production of H2O2 vs H2O) of these catalysts are provided, along with suggested methods for accurately comparing catalysts of different metals and ligand scaffolds that were examined under different experimental conditions.},
doi = {10.1021/acs.chemrev.7b00542},
journal = {Chemical Reviews},
number = 5,
volume = 118,
place = {United States},
year = {2018},
month = {3}
}

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