Water film-mediated mineralogical transformations and photocatalytic reactions

Sammanfattning: Mineral particles capture water vapor in the atmosphere in the form of water films that are only few monolayers thick. Water films form nanoscale hydration environments that mediate a wide range of important reactions in nature and technology. This thesis explored two important phenomena that commonly occur within the confines of water films: mineralogical transformations (Topic 1) and photocatalytic decomposition of organics (Topic 2). These transformations were chiefly identified by vibrational spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and (Transmission and Scanning) electron microscopy. Interpretations of reaction mechanisms were partially supported by chemometrics, kinetic and thermodynamic modeling, as well as molecular simulations.Mineralogical transformations (Topic 1) resolved in this thesis involved the hydroxylation (Papers I, II) and carbonation (Paper III) of periclase (MgO), and the oxidation of rhodochrosite (MnCO3) (Paper IV). Two types of MgO nanocubes with contrasting physical properties were used to resolve nucleation- and diffusion-limited hydroxylation reactions to brucite and carbonation reactions to amorphous magnesium carbonate (AMC). While nucleation-limited reactions completely transformed (8 nm) small and aggregated MgO nanocubes to brucite, the reactions became diffusion-limited in larger (32 nm) monodispersed MgO nanocubes because of brucite surface nanocoatings (Paper I). Additionally, brucite nanosheets grew under (GPa-level) crystallization pressures because of the important volumetric expansion of the reaction, which took place in a complex network of microporosity between the small and within the larger MgO nanocubes. Brucite stacking mechanisms, explored in Paper II, focused on the early stages of MgO-water interaction in water films of different thicknesses. These were suggested to involve the stacking and (epitaxial-like) growth of precursor Mg(OH)2 nanosheets in water films. Carbonation reactions explored in Paper III completely hampered hydroxylation reactions studied in Papers I and II, and produced AMC nanocoatings grown over an unreacted MgO core. Finally, oxidation-driven reactions involving rhodochrosite in Paper IV produced MnO2, Mn3O4, and MnOOH nanocoatings with growth rates being scaled with water loadings.Photocatalytic decomposition reactions of organics (Topic 2) were focused on the case of oxalate bound to TiO2 nanoparticles (Paper V). Photodecomposition rates scaled with humidity in oxygenated water films, and were explained by the combination of hole transfer (HT), ligand-to-metal charge transfer (LMCT), and the formation of hydroxyl radicals and reactive oxygen species. Decreasing rates in oxygen-free water films were, on the other hand, explained by water-driven charge localization, which eventually limited radical production and charge transfers via HT and LMCT. The reactions involved limited HT and LMCT processes which also competed with a charge recombination process across all humidity ranges.This thesis provides new insight into two key types of transformations mediated by water films on minerals. This knowledge can be used to understand the reactivity of mineral (nano)particles exposed to variations in atmospheric humidity and oxygen content, which are both highly relevant to a wide range of settings in nature and technology. It can also advance new ideas in the study of mineral growth, especially within the confines of nanometer-thick water films.