Search for: All records

Cooperativity and non-additive interactions play central roles in the unusual and surprising behavior of water. A host of reactive oxygen species (ROS) including the hydroxyl radical •OH, superoxide radical anion (O2–•), hydroperoxide radical (HO2•), singlet oxygen (1O2), and also the more recently discussed water radical cation/anion pair (H2O+•/H2O–•) all add to the more familiar acid/base chemical pathways tread by hydronium (H3O+) and hydroxide (OH–). This is amplified in surface science because interfacial water – whether found at the gas/liquid, gas/solid, or liquid/solid interface – poses yet more unique behavior. This review explores the unexpected chemistry associated with ambient temperature aqueous interfaces much of which is mediated not only by ions and neutrals as expected, but also radical species. Water microdroplets catalyze numerous reactions and can also support simultaneous oxidation and reduction reactions through the production of reactive intermediates that owe their existence to the unique influence of the air/water or oil/water interface. Interfacial water influences and is influenced by the ubiquitous phenomenon of contact electrification, a manifestation of spontaneous symmetry breaking. The mechanisms of chemistry not only on and in microdroplets but also at the gas/solid and liquid/solid interfaces rely on a broad set of chemical transformations mediated by radicals. Furthermore, because aqueous macro- and micro-interfaces are ubiquitous on Earth, we find that water radical-mediated chemistry has applications to atmospheric chemistry, geochemistry, mineral weathering, pre-biotic chemistry, enhanced enzyme performance, wastewater remediation, public health, mechanochemistry, and potentially novel routes to pharmaceuticals. 

Synthetic amorphous silica is a common food additive and a popular cosmetic ingredient. Mesoporous silica particles are also widely studied for their potential use in drug delivery and imaging applications because of their unique properties, such as tunable pore sizes, large surfaces areas, and assumed biocompatibility. Such a nanomaterial, when consisting of pure silicon dioxide, is generally considered to be chemically inert, but in this study, we showed that oxidation yields for different compounds were facilitated by simply incubating aqueous solutions with pure silica particles. Three thiol-containing molecules, L-cysteine, glutathione, and D-penicillamine, were studied separately, and it was found that more than 95% of oxidation happened after incubating any of these compounds with mesoporous silica particles in the dark for a day at room temperature. Oxidation increased over incubation time, and more oxidation was found for particles having larger surface areas. For nonporous silica particles at submicron ranges, yields of oxidation were different based on the structures of molecules, correlating with steric hindrance while accessing surfaces. We propose that the silyloxy radical (SiO•) on silica surfaces is what facilitates oxidation. Density functional theory calculations were conducted for total energy changes for reactions between different aqueous species and silicon dioxide surfaces. These calculations identified two most plausible pathways of the lowest energy to generate SiO• radicals from water radical cations H₂O•⁺and hydroxyl radicals •OH, previously known to exist at water interfaces. 

Mechanochemistry initiated the reaction of hydrogen-terminated porous silicon (H/por-Si) powder with arginine. Samples were analyzed using Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), zeta potential, scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. Arginine, which was physisorbed onto the surface of por-Si, blue-shifted the peak PL intensity from ~630 nm for the H/por-Si to ~565 nm for arginine-coated por-Si. Grinding for 4 h reduced >80% of the initially 2–45 µm particles to <500 nm, but was observed to quench the PL. With appropriate rinsing and centrifugation, particles in the 100 nm range were isolated. Rinsing ground powder with water was required to remove the unreacted arginine. Without rinsing, excess arginine induced the aggregation of passivated particles. However, water reacted with the freshly ground por-Si powder producing H2. A zeta potential of +42 mV was measured for arginine-terminated por-Si particles dispersed in deionized water. This positive value was consistent with termination such that NH2 groups extended away from the surface. Furthermore, this result was confirmed by FTIR spectra, which suggested that arginine was bound to silicon through the formation of a covalent Si–O bond. 

Electroless etching of semiconductors has been elevated to an advanced micromachining process by the addition of a structured metal catalyst. Patterning of the catalyst by lithographic techniques facilitated the patterning of crystalline and polycrystalline wafer substrates. Galvanic deposition of metals on semiconductors has a natural tendency to produce nanoparticles rather than flat uniform films. This characteristic makes possible the etching of wafers and particles with arbitrary shape and size. While it has been widely recognized that spontaneous deposition of metal nanoparticles can be used in connection with etching to porosify wafers, it is also possible to produced nanostructured powders. Metal-assisted catalytic etching (MACE) can be controlled to produce (1) etch track pores with shapes and sizes closely related to the shape and size of the metal nanoparticle, (2) hierarchically porosified substrates exhibiting combinations of large etch track pores and mesopores, and (3) nanowires with either solid or mesoporous cores. This review discussed the mechanisms of porosification, processing advances, and the properties of the etch product with special emphasis on the etching of silicon powders.