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

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 10 4 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. Reactions at the interface between water and other phases play important roles in various chemical settings. Now, ultrafast phase-sensitive interface-selective vibrational spectroscopy has revealed that the photoionization of phenol can occur four orders of magnitude faster at the water surface than in the bulk aqueous phase.