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

Lyle, Hanna; Singh, Suryansh; Paolino, Michael; Vinogradov, Ilya; Cuk, Tanja

doi:10.1039/d1cp01760h

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

Journal Article · Thu Aug 19 00:00:00 EDT 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp01760h· OSTI ID:1831510

Lyle, Hanna ^[1]; Singh, Suryansh ^[2]; Paolino, Michael ^[2]; Vinogradov, Ilya ^[2]; ^[2]

Univ. of Colorado, Boulder, CO (United States); University of Colorado, Boulder
Univ. of Colorado, Boulder, CO (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018939

OSTI ID:: 1831510

Alternate ID(s):: OSTI ID: 1819789

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 44 Vol. 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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