Spontaneous generation of hydrogen peroxide from aqueous microdroplets

We show H₂O₂ is spontaneously produced from pure water by atomizing bulk water into microdroplets (1 μm to 20 µm in diameter). Production of H₂O₂, as assayed by H₂O₂-sensitve fluorescence dye peroxyfluor-1, increased with decreasing microdroplet size. Cleavage of 4-carboxyphenylboronic acid and conversion of phenylboronic acid to phenols in microdroplets further confirmed the generation of H₂O₂ The generated H₂O₂ concentration was ∼30 µM (∼1 part per million) as determined by titration with potassium titanium oxalate. Changing the spray gas to O₂ or bubbling O₂ decreased the yield of H₂O₂ in microdroplets, indicating that pure water microdroplets directly generate H₂O₂ without help from O₂ either in air surrounding the droplet or dissolved in water. We consider various possible mechanisms for H₂O₂ formation and report a number of different experiments exploring this issue. We suggest that hydroxyl radical (OH) recombination is the most likely source, in which OH is generated by loss of an electron from OH^- at or near the surface of the water microdroplet. This catalyst-free and voltage-free H₂O₂ production method provides innovative opportunities for green production of hydrogen peroxide.