Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

Synthesis of heterogeneous catalysts based on manganese oxides applied for the aerobic oxidation of p-hydroxybenzyl alcohol to p-hydroxybenzaldehyde

In order to synthesize p-hydroxybenzaldehyde from p-hydroxybenzyl alcohol under oxygen atmosphere, we prepared the new heterogeneous catalysts based on manganese oxides by in-situ growth method at different pH values. The crystal structure, phase composition, morphology, and surface groups of catalysts were characterized by powder X-ray diffraction, field emission electron scanning microscopy and Fourier transform infrared spectroscopy. According to the experimental results, the solution pH used for the preparation of the catalysts strongly affected their properties and their catalytic activities. When the pH was increased from 2 to 4, the a-Mn2O3 content increased with the dominant presence of the rod-like particles. The quantity of Mn on the surface also enhanced which might improve the conversion of p-hydroxybenzyl alcohol while maintaining the high selectivity to p-hydroxybenzaldehyde (about 70%). However, when the pH was highr than 4, the quantity of rod-like particles,a-Mn2O3 and surface Mn species decreased which lowered the catalytic activity.

Birnessite: A New Oxidant for Green Rust Formation

Iron and manganese are ubiquitous in the natural environment. FeII-FeIII layered double hydroxide, commonly called green rust (GR), and MnIII-MnIV birnessite (Bir) are also well known to be reactive solid compounds. Therefore, studying the chemical interactions between Fe and Mn species could contribute to understanding the interactions between their respective biogeochemical cycles. Moreover, ferromanganese solid compounds are potentially interesting materials for water treatment. Here, a {Fe(OH)2, FeIIaq} mixture was oxidized by Bir in sulphated aqueous media in the presence or absence of dissolved O2. In oxic conditions for an initial FeII/OH− ratio of 0.6, a single GR phase was obtained in a first step; the oxidation kinetics being faster than without Bir. In a second step, GR was oxidised into various final products, mainly in a spinel structure. A partial substitution of Fe by Mn species was suspected in both GR and the spinel. In anoxic condition, GR was also observed but other by-products were concomitantly formed. All the oxidation products were characterized by XRD, XPS, and Mössbauer spectroscopy. Hence, oxidation of FeII species by Bir can be considered as a new chemical pathway for producing ferromanganese spinels. Furthermore, these results suggest that Bir may participate in the formation of GR minerals.

Ultralow loading of nanostructured Mn species onto two-dimensional Co3O4 nanosheets for selective catalytic reduction of NOx with NH3

We report a facile method for dispersing Mn species onto two-dimensional Co3O4 nanosheets at the nanoscale for the selective catalytic reduction (SCR) of NOx with NH3.

Unravelling the efficient catalytic performance of ozone decomposition over nitrogen-doped manganese oxide catalysts under high humidity

Nitrogen-doped Mn species, coated with a carbon layer of several nanometers in thickness, for enhanced water vapor resistance.