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Title: The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy

Abstract

The conversion of diffusive forms of energy (electrical and light) into short, compact chemical bonds by catalytic reactions regularly involves moving a carrier from an environment that favors delocalization to one that favors localization. While delocalization lowers the energy of the carrier through its kinetic energy, localization creates a polarization around the carrier that traps it in a potential energy minimum. The trapped carrier and its local distortion—termed a polaron in solids—can play a role as a highly reactive intermediate within energy-storing catalytic reactions but is rarely discussed as such. Here, we present this perspective of the polaron as a catalytic intermediate through recent in situ and time-resolved spectroscopic investigations of photo-triggered electrochemical reactions at material surfaces. The focus is on hole-trapping at metal–oxygen bonds, denoted M–OH*, in the context of the oxygen evolution reaction (OER) from water. The potential energy surface for the hole-polaron defines the structural distortions from the periodic lattice and the resulting “active” site of catalysis. This perspective will highlight how current and future time-resolved, multi-modal probes can use spectroscopic signatures of M–OH* polarons to obtain kinetic and structural information on the individual reaction steps of OER. A particular motivation is to provide the background neededmore » for eventually relating this information to relevant catalytic descriptors by free energies. Lastly, the formation of the O–O chemical bond from the consumption of M–OH*, required to release O2 and store energy in H2, will be discussed as the next target for experimental investigations.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1831510
Alternate Identifier(s):
OSTI ID: 1819789
Grant/Contract Number:  
SC0018939
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 23; Journal Issue: 44; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lyle, Hanna, Singh, Suryansh, Paolino, Michael, Vinogradov, Ilya, and Cuk, Tanja. The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy. United States: N. p., 2021. Web. doi:10.1039/d1cp01760h.
Lyle, Hanna, Singh, Suryansh, Paolino, Michael, Vinogradov, Ilya, & Cuk, Tanja. The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy. United States. https://doi.org/10.1039/d1cp01760h
Lyle, Hanna, Singh, Suryansh, Paolino, Michael, Vinogradov, Ilya, and Cuk, Tanja. 2021. "The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy". United States. https://doi.org/10.1039/d1cp01760h. https://www.osti.gov/servlets/purl/1831510.
@article{osti_1831510,
title = {The electron-transfer intermediates of the oxygen evolution reaction (OER) as polarons by in situ spectroscopy},
author = {Lyle, Hanna and Singh, Suryansh and Paolino, Michael and Vinogradov, Ilya and Cuk, Tanja},
abstractNote = {The conversion of diffusive forms of energy (electrical and light) into short, compact chemical bonds by catalytic reactions regularly involves moving a carrier from an environment that favors delocalization to one that favors localization. While delocalization lowers the energy of the carrier through its kinetic energy, localization creates a polarization around the carrier that traps it in a potential energy minimum. The trapped carrier and its local distortion—termed a polaron in solids—can play a role as a highly reactive intermediate within energy-storing catalytic reactions but is rarely discussed as such. Here, we present this perspective of the polaron as a catalytic intermediate through recent in situ and time-resolved spectroscopic investigations of photo-triggered electrochemical reactions at material surfaces. The focus is on hole-trapping at metal–oxygen bonds, denoted M–OH*, in the context of the oxygen evolution reaction (OER) from water. The potential energy surface for the hole-polaron defines the structural distortions from the periodic lattice and the resulting “active” site of catalysis. This perspective will highlight how current and future time-resolved, multi-modal probes can use spectroscopic signatures of M–OH* polarons to obtain kinetic and structural information on the individual reaction steps of OER. A particular motivation is to provide the background needed for eventually relating this information to relevant catalytic descriptors by free energies. Lastly, the formation of the O–O chemical bond from the consumption of M–OH*, required to release O2 and store energy in H2, will be discussed as the next target for experimental investigations.},
doi = {10.1039/d1cp01760h},
url = {https://www.osti.gov/biblio/1831510}, journal = {Physical Chemistry Chemical Physics. PCCP},
issn = {1463-9076},
number = 44,
volume = 23,
place = {United States},
year = {Thu Aug 19 00:00:00 EDT 2021},
month = {Thu Aug 19 00:00:00 EDT 2021}
}

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