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The photochemical reaction of phenol becomes ultrafast at the air–water interface

Nature Chemistry volume 13, pages 306–311 (2021)Cite this article

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Abstract

Reactions at the interface between water and other phases play important roles in nature and in various chemical systems. Although some experimental and theoretical studies suggest that chemical reactions at water interfaces can be different from those in bulk water—for example, ‘on-water catalysis’ and the activation of photochemically inert fatty acids at the air–water interface upon photoexcitation—directly investigating these differences and generating molecular-level understanding has proved difficult. Here, we report on the direct probing of a photochemical reaction occurring at the air–water interface, using ultrafast phase-sensitive interface-selective nonlinear vibrational spectroscopy. The femtosecond time-resolved data obtained clearly show that the photoionization reaction of phenol proceeds 104 times faster at the water surface than in the bulk aqueous phase (upon irradiation with photons with the same energy). This finding demonstrates that photochemical reactions at water interfaces are very different from those in bulk water, reflecting distinct reaction environments at the interface.

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Fig. 1: Experimental scheme for UV-TR-HD-VSFG of phenol at the air–water interface.
Fig. 2: Steady-state vibrational Imχ(2) spectra of the air–water and air–phenol aqueous solution interfaces.
Fig. 3: Time-resolved vibrational Imχ(2) spectra of the air–phenol aqueous solution interface after UV (267 nm) excitation.
Fig. 4: Spectra of the three transients observed with photoexcitation of phenol at the water interface.
Fig. 5: Photochemical dynamics of phenol excited by 267-nm light at the air–water interface and in bulk water.

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Data availability

The data in Figs. 2–4 and Supplementary Figs. 2–5 are provided as Microsoft Excel files linked in the source data for this Article. Source data are provided with this paper.

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Acknowledgements

This work was supported by JSPS KAKENHI grants JP25104005 and JP18H05265. R.K. acknowledges support form the Special Postdoctoral Researchers (SPDR) programme of RIKEN.

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Author notes

  1. Ryoji Kusaka

    Present address: Nuclear Science and Engineering Center, Japan Atomic Energy Agency, Tokai, Ibaraki, Japan

Authors and Affiliations

  1. Molecular Spectroscopy Laboratory, RIKEN, Wako, Saitama, Japan

    Ryoji Kusaka, Satoshi Nihonyanagi & Tahei Tahara

  2. Ultrafast spectroscopy Research Team, RIKEN Center for Advanced Photonics, Wako, Saitama, Japan

    Satoshi Nihonyanagi & Tahei Tahara

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  1. Ryoji Kusaka
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Contributions

R.K., S.N. and T.T. designed the research. R.K. performed the experiment and analysed the data. R.K., S.N. and T.T. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Tahei Tahara.

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Peer review information Nature Chemistry thanks Robert Walker and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Kusaka, R., Nihonyanagi, S. & Tahara, T. The photochemical reaction of phenol becomes ultrafast at the air–water interface. Nat. Chem. 13, 306–311 (2021). https://doi.org/10.1038/s41557-020-00619-5

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