Zeolite-dye micro lasers

We present a new class of micro lasers based on nanoporous molecular sieve host-guest systems. Organic dye guest molecules of 1-Ethyl-4-(4-(p-Dimethylaminophenyl)-1,3-butadienyl)-pyridinium Perchlorat were inserted into the 0.73-nm-wide channel pores of a zeolite AlPO$_4$-5 host. The zeolitic micro crystal compounds where hydrothermally synthesized according to a particular host-guest chemical process. The dye molecules are found not only to be aligned along the host channel axis, but to be oriented as well. Single mode laser emission at 687 nm was obtained from a whispering gallery mode oscillating in a 8-$\mu$m-diameter monolithic micro resonator, in which the field is confined by total internal reflection at the natural hexagonal boundaries inside the zeolitic microcrystals.Comment: Accepted for publication in Phys. Rev. Let

Capillary Condensation, Freezing, and Melting in Silica Nanopores: A Sorption Isotherm and Scanning Calorimetry Study on Nitrogen in Mesoporous SBA-15

Condensation, melting and freezing of nitrogen in a powder of mesoporous silica grains (SBA-15) has been studied by combined volumetric sorption isotherm and scanning calorimetry measurements. Within the mean field model of Saam and Cole for vapor condensation in cylindrical pores a liquid nitrogen sorption isotherm is well described by a bimodal pore radius distribution. It encompasses a narrow peak centered at 3.3 nm, typical of tubular mesopores, and a significantly broader peak characteristic of micropores, located at 1 nm. The material condensed in the micropores as well as the first two adsorbed monolayers in the mesopores do not exhibit any caloric anomaly. The solidification and melting transformation affects only the pore condensate beyond approx. the second monolayer of the mesopores. Here, interfacial melting leads to a single peak in the specific heat measurements. Homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the mesopores result in a caloric freezing anomaly similarly complex and dependent on the thermal history as has been observed for argon in SBA-15. The axial propagation of the crystallization in pore space is more effective in the case of nitrogen than previously observed for argon, which we attribute to differences in the crystalline textures of the pore solids.Comment: 10 pages, 7 figure

Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition

The possible role of ammonia in a future energy infrastructure is discussed. The review is focused on the catalytic decomposition of ammonia as a key step. Other aspects, such as the catalytic removal of ammonia from gasification product gas or direct ammonia fuel cells, are highlighted as well. The more general question of the integration of ammonia in an infrastructure is also covered

Fingerprinting the magnetic behavior of antiferromagnetic nanostructures using remanent magnetization curves

Antiferromagnetic (AF) nanostructures from Co3O4, CoO and Cr2O3 were prepared by the nanocasting method and were characterized magnetometrically. The field and temperature dependent magnetization data suggests that the nanostructures consist of a core-shell structure. The core behaves as a regular antiferromagnet and the shell as a two-dimensional diluted antiferromagnet in a field (2d DAFF) as previously shown on Co3O4 nanowires [Benitez et al., Phys. Rev. Lett. 101, 097206 (2008)]. Here we present a more general picture on three different material systems, i.e. Co3O4, CoO and Cr2O3. In particular we consider the thermoremanent (TRM) and the isothermoremanent (IRM) magnetization curves as "fingerprints" in order to identify the irreversible magnetization contribution originating from the shells. The TRM/IRM fingerprints are compared to those of superparamagnetic systems, superspin glasses and 3d DAFFs. We demonstrate that TRM/IRM vs. H plots are generally useful fingerprints to identify irreversible magnetization contributions encountered in particular in nanomagnets.Comment: submitted to PR

Advancing Critical Chemical Processes for a Sustainable Future: Challenges for Industry and the Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT)

Catalysis is involved in around 85 % of manufacturing industry and contributes an estimated 25 % to the global domestic product, with the majority of the processes relying on heterogeneous catalysis. Despite the importance in different global segments, the fundamental understanding of heterogeneously catalysed processes lags substantially behind that achieved in other fields. The newly established Max Planck–Cardiff Centre on the Fundamentals of Heterogeneous Catalysis (FUNCAT) targets innovative concepts that could contribute to the scientific developments needed in the research field to achieve net zero greenhouse gas emissions in the chemical industries. This Viewpoint Article presents some of our research activities and visions on the current and future challenges of heterogeneous catalysis regarding green industry and the circular economy by focusing explicitly on critical processes. Namely, hydrogen production, ammonia synthesis, and carbon dioxide reduction, along with new aspects of acetylene chemistry

Алгоритмы и программное обеспечение идентификации временных конструкций в слабоструктурированных электронных медицинских текстах

Работа направлена на повышение эффективности анализа электронных медицинских карт (ЭМК) с помощью разработки инструментов автоматического извлечения временных конструкций из медицинской документации. Полученные инструменты позволят перенести данные конструкции на временную шкалу и представить их в удобном для медицинских сотрудников виде.The work is aimed at increasing the efficiency of the analysis of electronic medical records (EMR) by developing tools for the automatic extraction of temporary structures from medical records. The resulting tools will allow doctors to transfer these structures to the timeline and present them in a form convenient for medical staff

Electronic structure and optical properties of lightweight metal hydrides

We study the electronic structures and dielectric functions of the simple hydrides LiH, NaH, MgH2 and AlH3, and the complex hydrides Li3AlH6, Na3AlH6, LiAlH4, NaAlH4 and Mg(AlH4)2, using first principles density functional theory and GW calculations. All these compounds are large gap insulators with GW single particle band gaps varying from 3.5 eV in AlH3 to 6.5 eV in the MAlH4 compounds. The valence bands are dominated by the hydrogen atoms, whereas the conduction bands have mixed contributions from the hydrogens and the metal cations. The electronic structure of the aluminium compounds is determined mainly by aluminium hydride complexes and their mutual interactions. Despite considerable differences between the band structures and the band gaps of the various compounds, their optical responses are qualitatively similar. In most of the spectra the optical absorption rises sharply above 6 eV and has a strong peak around 8 eV. The quantitative differences in the optical spectra are interpreted in terms of the structure and the electronic structure of the compounds.Comment: 13 pages, 10 figure

Reactivity of Metal Catalysts in Glucose–Fructose Conversion

A joint experimental and computational study on the glucose–fructose conversion in water is reported. The reactivity of different metal catalysts (CrCl3, AlCl3, CuCl2, FeCl3, and MgCl2) was analyzed. Experimentally, CrCl3 and AlCl3 achieved the best glucose conversion rates, CuCl2 and FeCl3 were only mediocre catalysts, and MgCl2 was inactive. To explain these differences in reactivity, DFT calculations were performed for various metal complexes. The computed mechanism consists of two proton transfers and a hydrogen-atom transfer; the latter was the rate-determining step for all catalysts. The computational results were consistent with the experimental findings and rationalized the observed differences in the behavior of the metal catalysts. To be an efficient catalyst, a metal complex should satisfy the following criteria: moderate Brønsted and Lewis acidity (pKa=4–6), coordination with either water or weaker σ donors, energetically low-lying unoccupied orbitals, compact transition-state structures, and the ability for complexation of glucose. Thus, the reactivity of the metal catalysts in water is governed by many factors, not just the Lewis acidity