RESUMO
Considering the alarming scenario of climate change, CO2 hydrogenation to methanol is considered a key process for phasing out fossil fuels by means of CO2 utilization. In this context, MoS2 catalysts have recently shown to be promising catalysts for this reaction, especially in the presence of abundant basal-plane sulfur vacancies and due to synergistic mechanisms with other phases. In this work, Mn-promoted MoS2 prepared by a hydrothermal method presents considerable selectivity for CO2 hydrogenation to methanol in comparison with pure MoS2 and other promoters such as K and Co. Interestingly, if CO is used as a carbon source for the reaction, methanol production is remarkably lower, which suggests the absence of a CO intermediate during CO2 hydrogenation to methanol. After optimization of synthesis parameters, a methanol selectivity of 64% is achieved at a CO2 conversion of 2.8% under 180 °C. According to material characterization by X-ray Diffraction and X-ray Absorption, the Mn promoter is present mainly in the form of MnO and MnCO3 phases, with the latter undergoing convertion to MnO upon H2 pretreatment. However, following exposure to reaction conditions, X-ray photoelectron spectroscopy suggests that higher oxidation states of Mn may be present at the surface, suggesting that the improved catalytic activity for CO2 hydrogenation to methanol arises from a synergy between MoS2 and MnOx at the catalyst surface.
RESUMO
Heterogeneous ice nucleation plays an important role in many environmental processes such as ice cloud formation, freezing of water bodies or biological freeze protection in the cryosphere. New information is needed about the seasonal availability, nature, and activity of ice nucleating particles (INPs) in alpine environments. These INPs trigger the phase transition from liquid water to solid ice at elevated subzero temperatures. We collected water samples from a series of alpine rivers and lakes (two valleys and their rivers, an artificial pond, and a natural lake system) in Obergurgl, Austria in June 2016, July 2016, November 2016, and May 2017. Each alpine river and lake was sampled multiple times across different seasons, depending on site access during different times of the year. Water samples were filtered through a 0.22 µm membrane filter to separate microbial INPs from the water, and both fractions were analyzed for ice nucleation activity (INA) by an emulsion freezing method. Microorganisms were cultured from the filters, and the cultures then analyzed for INA. Portions of the filtered samples were concentrated by lyophilization to observe potential enhancement of INA. Two sediment samples were taken as reference points for inorganic INPs. Sub-micron INPs were observed in all of the alpine water sources studied, and a seasonal shift to a higher fraction of microbial ice nucleators cultured on selective media was observed during the winter collections. Particles larger than 0.22 µm showed INA, and microbes were cultured from this fraction. Results from 60 samples gave evidence of a seasonal change in INA, presence of submicrometer INPs, and show the abundance of culturable microorganisms, with late spring and early summer showing the most active biological INPs. With additional future research on this topic ski resorts could make use of such knowledge of geographical and seasonal trends of microbial INPs in freshwater habitats in order to improve the production of artificial snow.
