Impact of Particle Aggregation on Nanoparticle Reactivity
The prevalence of nanoparticles in the environment is expected to grow in the coming years due to their increasing pervasiveness in consumer and industrial applications. Once released into the environment, nanoparticles encounter conditions of pH, salinity, UV light, and other solution conditions that may alter their surface characteristics and lead to aggregation. The unique properties that make nanoparticles desirable are a direct consequence of their size and increased surface area. Therefore, it is critical to recognize how aggregation alters the reactive properties of nanomaterials, if we wish to understand how these properties are going to behave once released into the environment. The size and structure of nanoparticle aggregates depend on surrounding conditions, including hydrodynamic ones. Depending on these conditions, aggregates can be large or small, tightly packed or loosely bound. Characterizing and measuring these changes to aggregate morphology is important to understanding the impact of aggregation on nanoparticle reactive properties. Examples of decreased reactivity due to aggregation include the case where tightly packed aggregates have fewer available surface sites compared to loosely packed ones; also, photocatalytic particles embedded in the center of large aggregates will experience less light when compared to particles embedded in small aggregates. However, aggregation also results in an increase in solid-solid interfaces between nanoparticles. This can result in increased energy transfer between neighboring particles, surface passivation, and altered surface tension. These phenomena can lead to an increase in reactivity. The goal of this thesis is to examine the impacts of aggregation on the reactivity of a select group of nanomaterials. Additionally, we examined how aggregation impacts the removal efficiency of fullerene nanoparticles using membrane filtration.
The materials we selected to study include ZnS - a metal chalcogenide nanoparticle that photoluminesces after exposure to UV; TiO2 and ZnO nanoparticles - photocatalytic nanoparticles that generate reactive oxygen species upon UV irradition; and, fullerene nanoparticles used in the filtration experiments, selected for their potential use, small size, and surface chemistry. Our primary methods used to characterize particle and aggregate characteristics include dynamic light scattering used to describe particle size, static light scattering used to characterize aggregate structure (fractal dimension), transmission electron microscopy used to verify primary particle sizes, and electrophoretic mobility measurements to evaluate suspension stability. The reactive property of ZnS that was measured as a function of aggregation was photoluminescence, which was measured using a spectrofluorometer. The reactive property of TiO2 and ZnO that was studied was their ability to generate hydroxyl radicals; these were measured by employing a fluorescent probe that becomes luminescent upon interaction with the hydroxyl radical. To detect the presence of fullerene nanoparticles and calculate removal efficiencies, we used total organic carbon measurements. Additionally, we used UV-vis spectroscopy to approximate the impact of particle shadowing in TiO2 and ZnO aggregates, and Fourier transformed infrared spectroscopy to determine how different electrolytes interact with fullerene surface groups.
Our findings indicate that the impact of aggregation on nanoparticle reactivity is material specific. ZnS nanoparticles exhibit a 2-fold increase in band-edge photoluminescence alongside a significant decrease in defect-site photoluminescence. This is attributed to aggregate size-dependent surface tension. Additionally, we used photoluminescence measurements to develop a new method for calculating the critical coagulation concentration of a nanoparticle suspension.
The ability of both TiO2 and ZnO to generate hydroxyl radicals was significantly hampered by aggregation. The decline in hydroxyl radical generation could be attributed to two key parameters. First, increased aggregate size was associated with increased particle shadowing, as determined from the observed decrease in the rate of optically induced transitions. Secondly, aggregate structure was associated both with increased shadowing (denser aggregates exhibited more shadowing than similarly sized loose aggregates), and with an increase in radical quenching on neighboring particle surfaces in an aggregate.
Aggregation had a positive impact on hydroxylated fullerene membrane separation, increasing removal efficiency to around 80%, regardless of transmembrane pressure. However, the type of electrolyte used determined whether aggregation was successful at increasing removal. Divalent ions, capable of forming strong covalent bonds with surface oxygen groups, increased removal efficiency and made it pressure insensitive. In contrast, monovalent ions increased removal efficiency slightly, but maintained the pressure dependence of the removal efficiency. Evidence is presented to support the hypothesis that divalently aggregated hydroxylated fullerenes deform under increased pressure and partially penetrate the membrane.
Finally, nanoparticle reactive properties depend on the primary particle aggregation state. Both size and structure are key factors when evaluating nanomaterial reactivity under aggregation-inducing conditions. However, the impact of aggregation is not easily predicted. Some materials exhibit a decreased reactivity while others experience an increase. Therefore, the impact of aggregation on nanoparticle reactive properties must be evaluated on a material-by-material basis, while considering all of the particle and aggregate characteristics as well as environmental ones.
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