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Abstract

Dissolution behavior of isolated and aggregated hematite particles in 10, 36, and 103 nm, respectively, was investigated using in situ liquid cell transmission microscopy (LCTEM). The high spatial and temporal resolution of LCTEM enables us to differentiate the respective effects of primary particle size, crystal defects, and aggregation state on particle dissolution. At similar electron-beam irradiation parameters, the initial surface-area normalized dissolution rates (RSA,Int) of isolated 10, 36, and 103 nm particles are 4.64 ± 3.60, 0.91 ± 0.44, and 0.24 ± 0.04 mg m–2 s–1, respectively. Interface free energy, calculated from the measured RSA,Int, decreases with the decreasing primary particle size. No preferential etching occurs on 10 nm, defect-free nanoparticles, whereas dissolution preferentially originates from crystal defects on 103 nm particles. In dissolution of aggregated particles, dissolution occurs more rapidly on the particles that are more accessible to bulk solution than the others inside the aggregate. As dissolution proceeds, dendritic aggregates break into several smaller aggregates that respectively shrink into even smaller and more compact aggregates, followed by reaggregation together. This study directly shows microscopic dissolution behavior of isolated and aggregated particles in different primary particle sizes, which is important to understand bioavailability, transport, and fate of nanoparticles in aquatic systems.

Impact Statement

The dissolution and degradation of nanomaterials (both naturally occurring and man-made) can have a significant impact the environment. LC-TEM enables dynamic processes such as nanoparticle degradation to be observed in real-time with high temporal and spatial resolution.  Using hematite nanoparticles of 10, 36 and 103 nms, researchers were able to drive beam induced dissolution of the nanoparticles in a solution to study the effect of size, defects and aggregation on the rate and mechanism of particle dissolution.