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.

本综述旨在批判性地分析水界面化学反应的新兴领域。自从发现所谓的“水上催化”以来，这一主题发展迅速，暗指水表面或其与疏水介质界面的反应急剧加速。我们回顾了大气化学和合成有机化学领域的关键实验研究，以及探索生命起源的相关研究，以展示这一现象的重要性。还讨论了这些过程的物理化学方面，例如水界面吸附和溶剂化过程的结构、动力学和热力学。我们还介绍了旨在解释界面催化的基本理论，以及先进的从头算分子动力学模拟的结果。