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Molecular reactions at aqueous interfaces

Abstract

This Review aims to critically analyse the emerging field of chemical reactivity at aqueous interfaces. The subject has evolved rapidly since the discovery of the so-called ‘on-water catalysis’, alluding to the dramatic acceleration of reactions at the surface of water or at its interface with hydrophobic media. We review critical experimental studies in the fields of atmospheric and synthetic organic chemistry, as well as related research exploring the origins of life, to showcase the importance of this phenomenon. The physico-chemical aspects of these processes, such as the structure, dynamics and thermodynamics of adsorption and solvation processes at aqueous interfaces, are also discussed. We also present the basic theories intended to explain interface catalysis, followed by the results of advanced ab initio molecular-dynamics simulations. Although some topics addressed here have already been the focus of previous reviews, we aim at highlighting their interconnection across diverse disciplines, providing a common perspective that would help us to identify the most fundamental issues still incompletely understood in this fast-moving field.

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Fig. 1: Examples of aqueous interfaces and interfacial processes.
Fig. 2: Schematic structure of the water surface.
Fig. 3: Thermodynamics of solvation at aqueous interfaces.
Fig. 4: Solute at the air–water interface.
Fig. 5: Reactant molecular orbitals at the air–water interface.
Fig. 6: Molecular-dynamics simulations of reactions at the air–water interface.

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Acknowledgements

M.F.R.-L. and M.T.C.M.-C. are grateful to the French CINES (project lct2550) for providing computational resources. J.M.A. thanks the Generalitat de Catalunya (grant 2017SGR348) for financial support.

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All authors contributed to researching data for the article, discussion of content, and review and editing of the manuscript before submission. M.F.R.-L. wrote the initial version of the manuscript.

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Correspondence to Manuel F. Ruiz-Lopez.

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Nature Reviews Chemistry thanks H. Mishra and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Ruiz-Lopez, M.F., Francisco, J.S., Martins-Costa, M.T.C. et al. Molecular reactions at aqueous interfaces. Nat Rev Chem 4, 459–475 (2020). https://doi.org/10.1038/s41570-020-0203-2

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