Spontaneous Reduction by One Electron on Water Microdroplets Facilitates Direct Carboxylation with CO₂

Recent advances in microdroplet chemistry have shown that chemical reactions in water microdroplets can be accelerated by several orders of magnitude compared to the same reactions in bulk water. Among the large plethora of unique properties of microdroplets, an especially intriguing one is the strong reducing power that can be sometimes as high as alkali metals as a result of the spontaneously generated electrons. In this study, we design a catalyst-free strategy that takes advantage of the reducing ability of water microdroplets to reduce a certain molecule, and the reduced form of that molecule can convert CO₂ into value-added products. By spraying the water solution of C₆F₅I into microdroplets, an exotic and fragile radical anion, C₆F₅I^•-, is observed, where the excess electron counter-intuitively locates on the σ* antibonding orbital of the C-I bond as evidenced by anion photoelectron spectroscopy. This electron weakens the C-I bond and causes the formation of C₆F₅^-, and the latter attacks the carbon atom on CO₂, forming the pentafluorobenzoate product, C₆F₅CO₂^-. This study provides a good example of strategically making use of the spontaneous properties of water microdroplets, and we anticipate that microdroplet chemistry will be a green avenue rich in new opportunities in CO₂ utilization.