TY - JOUR A1 - Ritter, B. A1 - Haida, P. A1 - Fink, F. A1 - Krahl, T. A1 - Gawlitza, Kornelia A1 - Rurack, Knut A1 - Scholz, G. A1 - Kemnitz, E. T1 - Novel and easy access to highly luminescent Eu and Tb doped ultra-small CaF2, SrF2 and BaF2 nanoparticles – structure and luminescence N2 - A universal fast and easy access at room temperature to transparent sols of nanoscopic Eu3+ and Tb3+ doped CaF2, SrF2 and BaF2 particles via the fluorolytic sol–gel synthesis route is presented. Monodisperse quasi-spherical nanoparticles with sizes of 3–20 nm are obtained with up to 40% rare earth doping showing red or green luminescence. In the beginning luminescence quenching effects are only observed for the highest content, which demonstrates the unique and outstanding properties of these materials. From CaF2:Eu10 via SrF2:Eu10 to BaF2:Eu10 a steady increase of the luminescence intensity and lifetime occurs by a factor of ≈2; the photoluminescence quantum yield increases by 29 to 35% due to the lower phonon energy of the matrix. The fast formation process of the particles within fractions of seconds is clearly visualized by exploiting appropriate luminescence processes during the synthesis. Multiply doped particles are also available by this method. Fine tuning of the luminescence properties is achieved by variation of the Ca-to-Sr ratio. Co-doping with Ce3+ and Tb3+ results in a huge increase (>50 times) of the green luminescence intensity due to energy transfer Ce3+ → Tb3+. In this case, the luminescence intensity is higher for CaF2 than for SrF2, due to a lower spatial distance of the rare earth ions. KW - Luminescence materials KW - Alkaline earth metal fluorides KW - Fluorolytic sol–gel synthesis PY - 2017 U6 - https://doi.org/10.1039/C6DT04711D VL - 46 IS - 9 SP - 2925 EP - 2936 PB - Royal Society of Chemistry AN - OPUS4-39286 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - Emmerling, Franziska A1 - Kemnitz, E. T1 - Strontium-coordination polymers based on tetrafluorophthalic and phthalic acids: mechanochemical synthesis, ab initio structures determination, and spectroscopic characterization N2 - Two strontium-based dicarboxylate systems [Sr(oBDC-F4)(H2O)2] (1) and [{Sr(oBDC)(H2O)2)·H2O] (2) were synthesized mechanochemically via milling of Sr(OH)2·8H2O with tetrafluorophthalic acid (H2oBDC-F4) or phthalic acid (H2oBDC), respectively. The new structures were determined ab initio from the powder X-ray diffraction (PXRD) data. Both compounds 1 and 2 crystallize in the monoclinic space group P21 /c as two-dimensional coordination polymers (2D-CPs). The determined structures were validated by extended X-ray absorption (EXAFS) data. Compounds 1 and 2 show different thermal stabilities. The fluorinated CP 1 is decomposed at 300 °C while the nonfluorinated CP 2 transforms into a new phase after thermal treatment at 400 °C. The two hydrated CPs exhibit small surface areas which increase after the thermal posttreatment for 1 but remains unchanged for the dehydrated sample of 2. Dynamic vapor sorption (DVS) experiments indicate that both the dehydrated and hydrated samples of 2 depict no significant differences in their adsorption isotherms. The DVS of water indicates that the phase transition after thermal posttreatment of 2 is irreversible. KW - Mechanochemistry KW - XRD KW - NMR PY - 2017 U6 - https://doi.org/10.1039/c7dt02564e SN - 1477-9226 SN - 1477-9234 VL - 46 IS - 37 SP - 12574 EP - 12587 PB - The Royal Society of Chemistry CY - Cambridge AN - OPUS4-42261 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kjaervik, Marit A1 - Müller, Anja A1 - Dietrich, P. A1 - Thissen, A. A1 - Bahr, S. A1 - Ritter, B. A1 - Kemnitz, E. A1 - Unger, Wolfgang T1 - Detection of suspended nanoparticles with near-ambient pressure x-ray photoelectron spectroscopy N2 - Two systems of suspended nanoparticles have been studied with near-ambient pressure x-ray photoelectron spectroscopy: silver nanoparticles in water and strontium fluoride—calcium fluoride core-shell nanoparticles in ethylene glycol. The corresponding dry samples were measured under ultra high vacuum for comparison. The results obtained under near-ambient pressure were overall comparable to those obtained under ultra high vacuum, although measuring silver nanoparticles in water requires a high pass energy and a long acquisition time. A shift towards higher binding energies was found for the silver nanoparticles in aqueous Suspension compared to the corresponding dry sample, which can be assigned to a change of surface potential at the water-nanoparticle interface. The shell-thickness of the core-shell nanoparticles was estimated based on simulated spectra from the National Institute of Standards and Technology database for simulation of electron spectra for surface analysis. With the instrumental set-up presented in this paper, nanoparticle suspensions in a suitable Container can be directly inserted into the analysis chamber and measured without prior sample preparation. KW - Nanoparticles KW - Suspensions KW - Core-shell nanoparticles KW - NAP-XPS PY - 2017 U6 - https://doi.org/10.1088/1361-648X/aa8b9d SN - 1361-648X SN - 0953-8984 N1 - Geburtsname von Müller, Anja: Hermanns, A. - Birth name of Müller, Anja: Hermanns, A. VL - 29 IS - 47 SP - 474002, 1 EP - 474002, 9 PB - IOP Publishing CY - UK AN - OPUS4-42951 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Al-Terkawi, Abdal-Azim A1 - Scholz, G. A1 - de Oliveira Guilherme Buzanich, Ana A1 - Reinsch, Stefan A1 - Kemnitz, E. A1 - Emmerling, Franziska T1 - Ca- and Sr- tetrafluoroisophthalates: mechanochemical synthesis, characterization, and ab initio structure determination N2 - New fluorinated coordination polymers were prepared mechanochemically by milling the alkaline earth metal hydroxides MII(OH)2·xH2O (MII: Ca, Sr) with tetrafluoroisophthalic acid (H2mBDC-F4). The structures of [{Ca(mBDC-F4)(H2O)2}·H2O] and [{Sr(mBDC-F4)(H2O)2}·H2O] were determined based on ab initio calculations and their powder X-ray diffraction (PXRD) data. The compounds are isomorphous and crystallize in the orthorhombic space group P212121. The determined structures were validated by using extended X-ray absorption (EXAFS) data. The new materials were thoroughly characterized using elemental analysis, thermal analysis, magic angle spinning NMR, and attenuated total reflection-infrared spectroscopy. Further characterization methods such as BET, dynamic vapor sorption, and scanning electron microscopy imaging were also used. Our investigations indicate that mechanochemistry is an efficient method for preparing such materials. KW - Mechanochemistry KW - In situ KW - XRD KW - Coordination polymers PY - 2017 UR - http://pubs.rsc.org/-/content/articlehtml/2017/dt/c7dt00734e U6 - https://doi.org/10.1039/c7dt00734e VL - 46 IS - 18 SP - 6003 EP - 6012 AN - OPUS4-41516 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Meißner, G. A1 - Dirican, D. A1 - Jäger, Christian A1 - Braun, T. A1 - Kemnitz, E. T1 - Et3GeH versus Et3SiH: controlling reaction pathways in catalytic C–F bond activations at a nanoscopic aluminum chlorofluoride† N2 - Catalytic C–F bond activation reactions of mono- and polyfluoroalkanes at Lewis acidic amorphous aluminum chlorofluoride (ACF) are presented. The hydrogen sources Et3GeH or Et3SiH control the selectivity of the conversions. The immobilization of Et3GeH at ACF resulted in catalytic dehydrohalogenation reactions to yield olefins under very mild conditions. In contrast, if Et3SiH is immobilized at ACF, C–C coupling occured and the formation of Friedel–Crafts products was observed. MAS NMR spectroscopic studies revealed information about the surface binding of the substrates. KW - Vapor-phase hydrofluorination KW - Carbon-fluorine bonds KW - Vinyl fluoride KW - Phosphine-ligands KW - Room-temperature KW - Building-blocks KW - Etal-complexes KW - Germylium ions KW - Lewis-acids KW - Hydrodefluorination PY - 2017 U6 - https://doi.org/10.1039/c7cy00845g SN - 2044-4753 SN - 2044-4761 VL - 7 IS - 15 SP - 3348 EP - 3354 PB - The Royal Society of Chemistry AN - OPUS4-41836 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -