Facet-specific oxidation of Mn(II) and heterogeneous growth of manganese (oxyhydr)oxides on hematite nanoparticles

It is recognized that different facets of minerals vary distinctively in their chemical reactivity with aqueous solutions. However, detailed molecular and atomistic understandings of these phenomena are relatively limited. This study investigated the interaction of aqueous Mn2+ and dissolved oxygen on various facets of two morphology-types of iron oxide (hematite) nanocrystals. These interactions result in the oxidation of Mn(II) and heterogeneous growth of Mn(II)/Mn(III) and Mn(III) oxides. The nanoscale morphology and atomic structure of the manganese oxide products were characterized in detail. Our results, for the first time, directly demonstrate the facet-specific oxidation of Mn(II) and nucleation of Mn(II/III) oxides, followed by their epitaxial growth on hematite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron diffraction measurements reveal the growth of MnOx nanowires on {1 1 3} of hematite nanoplates (HNP) and {0 1 2} facets of hematite nanocubes (HNC), while the basal {0 0 1} facets on the HNP particles do not produce precipitates. The average oxidation states of the MnOx on HNP and HNC determined using electron energy-loss spectroscopy (EELS) show that both Mn(II) and Mn(III) are present. The mineral composition and growth mechanisms of MnOx catalyzed by HNP and HNC are similar. High-resolution TEM analysis reveals the presence of both hausmannite and manganite on HNP and HNC. The crystallographic relationship between the heterogeneously formed manganite with hematite, which has not been reported before, proves that hematite provides reaction sites and can function as an atomic template for the formation of MnOx nanowires. These findings advance our understanding of the redox chemistry and heterogeneous growth of minerals as controlled by the surficial structure of the substrate mineral. This has important geochemical implications as the catalytic growth of less common, highly reactive phases like MnOx are known to be consequential in complex natural and anthropogenic environments.