Disentangling the Roles of Dissolved Oxygen, Common Salts, and pH on the Spontaneous Hydrogen Peroxide Production in Water: No O2, No H2O2

Despite the mounting evidence proving that the air-water interface or the microdroplet geometry has nothing to do with the spontaneous formation of hydrogen peroxide (H2O2), the myth persists. Three recent studies by George and co-workers give credence to the myth by showing connections between the spontaneous formation of hydroxyl (HO) radicals and hydrogen peroxide (H2O2) in sprayed microdroplets with the solution pH, dissolved salts, nebulizing gas, and the gaseous environment. They report that among halides (chloride, bromide, and iodide), bromide dominates the H2O2 formation because of its ability to donate electrons. Also, they conclude that the H2O2 production at the air-water interface scales with waters alkalinity. In response, we apply a broad set of techniques, spanning NMR, potentiodynamic polarization, electron microscopy, and hydrogen peroxide assay kit (HPAK) fluorometry, to reexamine these claims. Our experiments reveal that regardless of the halide present in water, the air-water interface or the microdroplet geometry does not drive the H2O2 formation. It is the reduction of O2 at the solid-water interface that produces H2O2, i.e., in the absence of O2, no H2O2 is formed regardless of the halide ions. We explain the relative dependence of H2O2 concentrations on the halides based on their propensity to drive pitting corrosion (Chloride > Bromide > Iodide). As the pits appear in the passivating layer, exposing the metal, H2O2 is consumed in further oxidation. Next, we disprove the claim of alkalinity-driven H2O2 formation by demonstrating that aluminum and titanium surfaces produce more H2O2 in acidic and alkaline conditions, respectively. Taken together, these findings refute the conclusions of George and co-workers and others regarding spontaneous H2O2 generation at the air-water interface. The following mnemonic captures our conclusion: no O2, no H2O2.