Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Vinogradov, Ilya; Singh, Suryansh; Lyle, Hanna; Paolino, Michael; Mandal, Aritra; Rossmeisl, Jan; Cuk, Tanja

doi:10.1038/s41563-021-01118-9

Free energy difference to create the M-OH* intermediate of the oxygen evolution reaction by time-resolved optical spectroscopy

Journal Article · Mon Nov 01 00:00:00 EDT 2021 · Nature Materials

DOI:https://doi.org/10.1038/s41563-021-01118-9· OSTI ID:1831508

^[1]; Singh, Suryansh ^[2]; Lyle, Hanna ^[2]; Paolino, Michael ^[2]; ^[2]; ^[3]; ^[2]

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

Theoretical descriptors differentiate the catalytic activity of materials for the oxygen evolution reaction by the strength of oxygen binding in the reactive intermediate created upon electron transfer. Recently, time-resolved spectroscopy of a photo-electrochemically driven oxygen evolution reaction followed the vibrational and optical spectra of this intermediate, denoted M-OH*. However, these inherently kinetic experiments have not been connected to the relevant thermodynamic quantities. Here we discover that picosecond optical spectra of the Ti-OH* population on lightly doped SrTiO₃ are ordered by the surface hydroxylation. A Langmuir isotherm as a function of pH extracts an effective equilibrium constant relatable to the free energy difference of the first oxygen evolution reaction step. Thus, time-resolved spectroscopy of the catalytic surface reveals both kinetic and energetic information of elementary reaction steps, which provides a critical new connection between theory and experiment by which to tailor the pathway of water oxidation and other surface reactions.

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:: 1831508

Journal Information:: Nature Materials, Journal Name: Nature Materials Vol. 21; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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