arXiv subjects

Muzzamil Ahmad Eatoo

Publications and source records attributed to Muzzamil Ahmad Eatoo.

5 recordsLinked to original sources

arXiv2026

Resolving the Bubble Puzzle: Hydrogen Peroxide Formation Precedes Hydroxyl Radicals in Microbubbles and is Governed by Solid-Water Interfaces

An alternative explanation is presented for recent reports that attribute sustained chemiluminescence (CL) and electrochemiluminescence (ECL) from electrogenerated microbubbles on steel or copper electrodes in aqueous luminol solutions (over 2-30 V range) to the spontaneous formation of hydroxyl radicals at the gas-water interface. Our experiments with a broad set of electrodes, viz., steel, copper, aluminium, and platinum, reveal that while microbubbles can be electrogenerated on all electrodes, CL is exhibited by steel and Cu only and not by Al and Pt. These observations establish that the gas-water interface of microbubbles is not the site for hydroxyl radical generation (else CL would be recorded in all cases). Complementary quantification of H2O2 in these experiments reveals its electrode dependence as follows: Al > Cu > Steel > Pt. This establishes that depending on the electrode, H2O2 forms first, and in some cases, hydroxyl radicals are observed (i.e., where CL/ECL is seen). Experiments with NMR and EPR spectroscopy revealed that: (i) H2O2 formation occurs only when O2 is present in water; and (ii) while steel and copper generate hydroxyl radicals through 1-electron reduction of H2O2, Al does not promote one-electron reduction of H2O2 to generate hydroxyl radicals, and Pt preferentially promotes disproportionation of H2O2 to H2O and O2. In fact, we demonstrate that H2O2 and hydroxyl radicals can be observed at specific metal-water interfaces even without microbubbles, confirming that the solid surface is the reactive site. Therefore, this work affords electrode-based predictions of whether or not electrogenerated microbubbles would yield CL in luminol solutions and calls into question the notion of spontaneous formation of hydroxyl radicals at gas-water interfaces.

physics.chem-ph↗

arXiv2025

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.

cond-mat.soft↗

arXiv2024

Hydrogen peroxide forms spontaneously in water (bulk, film, or microdroplet) via reduction of dissolved oxygen at solid-water interface

Zare and co-workers have recently claimed that hydrogen peroxide is spontaneously generated on the air-water interface of sprayed microdroplets, i.e., that H2O2 forms without an external energy source or co-reactant or catalyst. Specifically, they find that the H2O2(aq) concentration in sprayed microdroplets increases by a factor of 3.5 (or 2.5) as the spray chamber's relative humidity (RH) is changed from 15% to 50% (or from 15% to 95%). Building on these results, they imply causation for the seasonality of viral infections arising from the RH-dependent H2O2 generation in environmental microdroplets. Here, we present an alternative explanation for their observations.

cond-mat.soft↗

arXiv2024

Why Some Metal Ions Spontaneously Form Nanoparticles in Water Microdroplets? Disentangling the Contributions of Air-Water Interface and Bulk Redox Chemistry

Water microdroplets containing 100 micromolar HAuCl4 have been shown to reduce gold ions into gold nanoparticles spontaneously. It has been suggested that this chemical transformation is driven by ultrahigh electric fields at the air-water interface, albeit without mechanistic insight. We investigated the fate of several metallic salts in water, methanol, ethanol, and acetonitrile in bulk and microdroplets. This revealed that when HAuCl4 (or PtCl4) is added to bulk water (or methanol or ethanol), metal NPs appear spontaneously. Over time, the nanoparticles grow in bulk, as evidenced by the solution's changing colors. If the same bulk solution is sprayed pneumatically and collected, the NP size has no significant enhancement. Interestingly, the reduction of metal ions is accompanied by the oxidation of water (or alcohols); however, these redox reactions are minimal in acetonitrile. We establish that the spontaneous reduction of metal ions is (i) not limited to water or gold ions, (ii) not driven by the air-water interface of microdroplets, and (iii) appears to be a general phenomenon for solvents containing hydroxyl groups. These results advance our understanding of liquids in general and should be relevant in soil chemistry, biogeochemistry, electrochemistry, and green chemistry.

cond-mat.soft↗

arXiv2023

Busting the Myth of Spontaneous Formation of H2O2 at the Air-Water Interface: Contributions of the Liquid-Solid Interface and Dissolved Oxygen Exposed

Recent reports on the spontaneous formation of H2O2(aq) at the air-water interface and the solid-water interface have been sensational. The speculated mechanism at the air-water interface is based on instantaneous ultrahigh electric fields and the micro-scale of droplets, whereas the solid-water interface is speculated to be the site for oxidation of water (or hydroxide ions) and reduction of the solid surface. We utilized 1H-NMR spectroscopy to investigate the effects of the nebulizing gas, the dissolved oxygen content, and solid substrates on the H2O2(aq) formation (detection limit 50 nM). Experiments revealed that contrary to the sensational claims, the air-water interface is not the site for H2O2(aq) formation; instead, it is the solid-water interface where H2O2(aq) is formed during the reduction of dissolved oxygen and oxidation of the solid surface. Curiously, the tendencies of solid substrates towards forming H2O2(aq) follow the classic Galvanic series. This report advances the current understanding of aquatic chemistry and should be relevant to corrosion science, surface science, and electrochemistry.

cond-mat.soft↗