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Title: Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions

Journal Article · · ACS Central Science
 [1];  [1];  [2];  [3];  [4];  [5];  [2];  [1]
  1. Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States
  2. Pacific Northwest National Laboratory (PNNL), Richland, Washington 99352, United States
  3. Department of Chemistry, University of South Florida, Tampa, Florida 33620, United States
  4. Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States
  5. Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States
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Improvement of electrocatalysts for the oxygen reduction reaction (ORR) is critical for the advancement of fuel cell technologies. Herein, we report a series of eleven soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s-1 to an unprecedented 2.2 x 106 s-1. These TOFs correlate with the ORR overpotential, which can be changed by modulating the ancillary ligand, by varying the reaction conditions or by changing the catalyst’s protonation state. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of the high overpotential. Computational studies indicate that the correlation is analogous to the volcano plot analysis developed for heterogeneous ORR materials. This unique parallel between homo- and heterogeneous ORR electrocatalysts allows a fundamental understanding of intrinsic barriers associated with the ORR, which can aid the design of new catalytic systems that operate at low overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Additional data is given in the Electronic Supporting Information.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1330399
Alternate ID(s):
OSTI ID: 1339858
Report Number(s):
PNNL-SA-117180
Journal Information:
ACS Central Science, Journal Name: ACS Central Science Vol. 2 Journal Issue: 11; ISSN 2374-7943
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 126 works
Citation information provided by
Web of Science

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