TY - JOUR A1 - Agirrezabal-Telleria, Iker A1 - Guo, Y. A1 - Hemmann, Felix A1 - Arias, P. L. A1 - Kemnitz, E. T1 - Dehydration of xylose and glucose to furan derivatives using bifunctional partially hydroxylated MgF2 catalysts and N2-stripping JF - Catalysis science & technology N2 - The current furfural production yield is low due to the use of non-selective homogeneous catalysts and expensive separation. In this work, partially hydroxylated MgF2 catalysts, synthesized using different water contents, were screened during xylose dehydration in water–toluene at 160 °C. The different Lewis/Brønsted ratios on the MgF2 catalysts showed that under-coordinated Mg can isomerize xylose to xylulose, whilst the surface OH-groups were responsible for the dehydration reactions. The presence of glucose as a co-carbohydrate reduced the furfural selectivity from 86 to 81%, whilst it also led to high 5-hydroxymethylfurfural selectivity. The tests catalyzed by MgF2 in combination with simultaneous N2-stripping showed that a furfural selectivity of 87% could be achieved using low xylose loadings. Moreover, the catalysts regenerated by H2O2 showed high activity during the dehydration tests in water–toluene at 160 °C. KW - Bifunctional MgF2 KW - Lewis/Bronsted KW - Carbohydrates KW - Furan derivatives KW - N2-stripping PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-305441 DO - https://doi.org/10.1039/c4cy00129j SN - 2044-4753 SN - 2044-4761 VL - 4 IS - 5 SP - 1357 EP - 1368 PB - RSC Publ. CY - Cambridge AN - OPUS4-30544 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ritter, B. A1 - Krahl, T. A1 - Rurack, Knut A1 - Kemnitz, E. T1 - Nanoscale CaF2 doped with Eu3+ and Tb3+ through fluorolytic sol-gel synthesis JF - Journal of materials chemistry C N2 - In this article, the high potential of the fluorolytic sol–gel process to synthesize nanoscopic rare earth-doped calcium fluoride sols is shown. Through a fluorolytic sol–gel process we manage to achieve spherical monodisperse ~5 nm sized nanoparticles using a simple and reproducible one-pot-wet chemical route at room temperature. The as-synthesized clear sols exhibit an intense red and green luminescence under UV excitation at room temperature. A spectroscopic study of the sols revealed the characteristic transitions 5D0 → 7FJ of Eu3+ and 5D4 → 7FJ of Tb3+, with 5D0 → 7F2 (611 nm) of Eu3+ and 5D4 → 7F4 (581 nm) of Tb3+ as the most prominent transitions. This facile synthetic strategy is also valuable for developing other luminescent nanoparticles. KW - Calciumfluorid KW - Europium KW - Lumineszenz KW - Nanopartikel KW - Sol-Gel-Synthese KW - Terbium PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-320120 DO - https://doi.org/10.1039/c4tc01073f SN - 2050-7526 SN - 2050-7534 VL - 2 IS - 40 SP - 8607 EP - 8613 PB - Royal Soc. of Chemistry CY - Cambridge AN - OPUS4-32012 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hemmann, Felix A1 - Jäger, Christian A1 - Kemnitz, E. T1 - Comparison of acidic site quantification methods for a series of nanoscopic aluminium hydroxide fluorides JF - RSC Advances N2 - Quantitative determination of acidic surface sites is highly important for the characterization of solid acids because the activity of a catalyst is often related to the concentration of these sites. A recently developed method using 15N Nuclear Magnetic Resonance spectroscopy (NMR) for the quantification of acidic Lewis and Brønsted sites has been tested for a series of nanoscopic aluminum hydroxide fluorides. Comparison with other methods for the quantitative determination of acidic sites shows that this 15N NMR quantification method is a promising technique for the comprehensive investigation of acidic sites. Three different acidic sites, one Brønsted and two Lewis sites, can be distinguished by their 15N chemical shifts of pyridine and simultaneously quantified under conditions corresponding to catalytic reaction conditions. Determination of the individual concentrations of acidic sites allows further insight into the catalytic process. It was found that the concentration of Brønsted sites correlates with catalyzed conversion of citronellal to isopulegol in the investigated series of catalysts. Additionally, investigations indicate that one of the Lewis sites become blocked during the reaction of citronellal. KW - Solid acids KW - TOF KW - NH3-TPD KW - Progressive catalyst poisoning KW - FTIR KW - Quantitative NMR KW - Solid state NMR PY - 2014 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-323280 DO - https://doi.org/10.1039/c4ra09477h SN - 2046-2069 VL - 4 IS - 100 SP - 56900 EP - 56909 PB - RSC Publishing CY - London AN - OPUS4-32328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -