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Photooxidation of the Phenolate Anion is Accelerated at the Water/Air Interface

Jordan, Caleb J.C.; Lowe, Eleanor A.; Verlet, Jan R.R.

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Authors

Caleb J.C. Jordan

Eleanor A. Lowe



Abstract

Molecular photodynamics can be dramatically affected at the water/air interface. Probing such dynamics is challenging, with product formation often probed indirectly through its interaction with interfacial water molecules using time-resolved and phase-sensitive vibrational sum-frequency generation (SFG). Here, the photoproduct formation of the phenolate anion at the water/air interface is probed directly using time-resolved electronic SFG and compared to transient absorption spectra in bulk water. The mechanisms are broadly similar, but 2 to 4 times faster at the surface. An additional decay is observed at the surface which can be assigned to either diffusion of hydrated electrons from the surface into the bulk or due to increased geminate recombination at the surface. These overall results are in stark contrast to phenol, where dynamics were observed to be 104 times faster and for which the hydrated electron was also a photoproduct. Our attempt to probe phenol showed no electron signal at the interface.

Citation

Jordan, C. J., Lowe, E. A., & Verlet, J. R. (2022). Photooxidation of the Phenolate Anion is Accelerated at the Water/Air Interface. Journal of the American Chemical Society, 144(31), 14012-14015. https://doi.org/10.1021/jacs.2c04935

Journal Article Type Article
Online Publication Date Jul 28, 2022
Publication Date Aug 10, 2022
Deposit Date Aug 18, 2022
Publicly Available Date Aug 18, 2022
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 144
Issue 31
Pages 14012-14015
DOI https://doi.org/10.1021/jacs.2c04935

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