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Title: Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis

Abstract

The development of advanced chemical-to-electrical energy conversions requires fast and efficient electrocatalysis of multielectron/multiproton reactions, such as the oxygen reduction reaction (ORR). Using molecular catalysts, correlations between the reaction rate and energy efficiency have recently been identified. Improved catalysis requires circumventing the rate versus overpotential trade-offs implied by such “scaling relationships.” Described here is an ORR system—using a soluble iron porphyrin and weak acids—with the best reported combination of rate and efficiency for a soluble ORR catalyst. This advance is achieved not by “breaking” scaling relationships but rather by combining two of them. Key to this behavior is a polycationic ligand, which enhances anionic ligand binding and changes the catalystE1/2. These results show how combining scaling relationships is a powerful way toward improved electrocatalysis.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1626058
Grant/Contract Number:  
FG02-00ER41132
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology - Other Topics

Citation Formats

Martin, Daniel J., Mercado, Brandon Q., and Mayer, James M.. Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis. United States: N. p., 2020. Web. https://doi.org/10.1126/sciadv.aaz3318.
Martin, Daniel J., Mercado, Brandon Q., & Mayer, James M.. Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis. United States. https://doi.org/10.1126/sciadv.aaz3318
Martin, Daniel J., Mercado, Brandon Q., and Mayer, James M.. Sun . "Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis". United States. https://doi.org/10.1126/sciadv.aaz3318. https://www.osti.gov/servlets/purl/1626058.
@article{osti_1626058,
title = {Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis},
author = {Martin, Daniel J. and Mercado, Brandon Q. and Mayer, James M.},
abstractNote = {The development of advanced chemical-to-electrical energy conversions requires fast and efficient electrocatalysis of multielectron/multiproton reactions, such as the oxygen reduction reaction (ORR). Using molecular catalysts, correlations between the reaction rate and energy efficiency have recently been identified. Improved catalysis requires circumventing the rate versus overpotential trade-offs implied by such “scaling relationships.” Described here is an ORR system—using a soluble iron porphyrin and weak acids—with the best reported combination of rate and efficiency for a soluble ORR catalyst. This advance is achieved not by “breaking” scaling relationships but rather by combining two of them. Key to this behavior is a polycationic ligand, which enhances anionic ligand binding and changes the catalystE1/2. These results show how combining scaling relationships is a powerful way toward improved electrocatalysis.},
doi = {10.1126/sciadv.aaz3318},
journal = {Science Advances},
number = 11,
volume = 6,
place = {United States},
year = {2020},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Fig. 1 Fig. 1: Catalytic system efficiencies, reaction mechanism, and structure of catalyst 1. (A) Plot of log(TOFmax)/$η$eff values and fits (dashed lines) for 1 (diamonds; data and conditions in Table 1) and for previously reported iron porphyrin [Fe(por)] catalysts (circles; 0.1 M [DMF-H+] in DMF or MeCN) (5). The uncertainties aremore » smaller than the data points. The yellow shading indicates an aspirational region. (B) Fe(por) catalyzed O2 reduction mechanism, as described in the main text. (C) Drawings of 1 and of the cation in the solid-state x-ray crystal structure, [1•2H2O]OTf5 (Fe, orange; N, blue; C, white; O, red; H atoms omitted for clarity; thermal ellipsoids at 50% probability).« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.