Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (32)
- Posterpräsentation (8)
- Vortrag (5)
- Beitrag zu einem Sammelband (2)
- Beitrag zu einem Tagungsband (1)
Schlagworte
- Mössbauer spectroscopy (9)
- Iron (3)
- Aluminium phosphate (2)
- Ash (2)
- High-spin molecule (2)
- Magnetite (2)
- Multiple spin transition (2)
- Multistability (2)
- Mössbauer (2)
- Mössbauer Spectroscopy (2)
Eingeladener Vortrag
- nein (5)
Hydrogenation of nitrate to nitrogen using Pd/Al2O3 catalysts promoted by a second metal offers a promising process for nitrate removal in drinking water treatment. This study was aimed to elucidate the nature and function of promoting tin species in PdSn/Al2O3 catalysts obtained in different preparation routes. On one hand, a parent Pd/Al2O3 catalyst was doped via impregnation with aqueous solutions of SnCl2 of different concentrations. On the other hand, the palladium surface of the same parent Pd/Al2O3 catalyst was modified via controlled surface reaction (CSR) with hexane solutions of Sn(C4H9)4. The structure of the different PdSn/Al2O3 catalysts was investigated by 119Sn-Mössbauer spectroscopy and by means of various chemisorption techniques (static and pulse chemisorption of H2 or CO, measurement of the differential heat of CO chemisorption, FTIR spectroscopy of CO chemisorption). Catalytic properties were studied in batch experiments under atmospheric pressure. Promoting of the Pd/Al2O3 catalyst by CSR resulted in catalysts with a significantly higher activity compared to PdSn/Al2O3 catalysts obtained via incipient wetness method. Obviously, Sn(II)-species being present in the latter in high portion inhibit the nitrate reduction on bimetallic PdSn ensembles.
CO chemisorption reflected a palladium site blocking by tin species in both kinds of catalysts and indirectly indicated the generation of palladiumtin ensembles. In case of the CSR preparation the palladium is alloyed by metallic tin.
The palladium surface is diluted by tin atoms, i.e. bimetallic PdSnx ensembles are generated which are able to adsorb and activate nitrate ions. There is an optimum of tin loading, i.e. the activity decreases and the undesired ammonium production in a site reaction increases when the surface becomes too tin rich. Sn(II) species, being preferentially present in catalysts obtained by SnCl2 impregnation also strongly modify the chemisorption properties of the palladium surface, but obviously these species inhibit the nitrate reduction on the bimetallic PdSn ensembles, which are also present in these catalysts.
Self-assembly of Fe(II) and the ditopic ligand 1,4-bis(2,2':6',2"-terpyridine-4'-yl)benzene results in equilibrium structures in solutions, so-called metallosupramolecular coordination polyelectrolytes (MEPEs). It is exceedingly difficult to characterize such macromolecular assemblies, because of the dynamic nature. Therefore, hardly any structural information is available for this type of material. Here, we show that from dilute solutions, where small aggregates predominate, it is possible to grow nanoscopic crystals at an interface. A near atomic resolution structure of MEPE is obtained by investigating the nanoscopic crystals with electron diffraction in combination with molecular modeling. The analysis reveals a primitive monoclinic unit cell (P21/c space group, a = 10.4 Å, b = 10.7 Å, c = 34.0 Å, α = γ = 90°, β = 95°, ρ = 1.26 g/cm³, and Z = 4). The MEPE forms linear rods, which are organized into sheets. Four sheets intersect the unit cell, while adjacent sheets are rotated by 90° with respect to each other. The pseudooctahedral coordination geometry of the Fe(II) centers is confirmed by Mössbauer spectroscopy. The combination of diffraction and molecular modeling presented here may be of general utility to address problems in structural materials science.
The Goldschmidt reaction (2Al+α-Fe2O3) was investigated both under mechanical and thermal activation by employing a combination of analytical methods such as ESR and Mössbauer spectroscopy, magnetic susceptibility, X-ray powder diffraction, and thermal analysis (TA). Both the mechanical treatment and the TA runs under air caused the reaction conditions of 'quiet redox reactions' due to a retarding effect and enabled a reaction study in a 'slow motion mode'. This allowed to establish distinct partial steps of the integral reaction process depending on the intensity of the mechanical impact, the educt composition, the gas phase composition, and, finally, the thermal excitation in the TA runs. Particular attention was payed to the role of the gas phase and to the reaction of aluminum with differently activated oxygen species. The phlegmatizing effect was traced back to the formation of Al2O3 coverages of the Al particles.
Reaction between an aqueous ethanol solution of tin(II) chloride and that of 4-propanoyl-2,4-dihydro-5-methyl-2-phenyl-3 H-pyrazol-3-one in the presence of O2 gave the compound cis-dichlorobis(4-propanoyl-2,4-dihydro-5-methyl-2-phenyl-3 H-pyrazol-3-onato) tin(IV) [(C26H26N4O4)SnCl2]. The compound has a six-coordinated SnIV centre in a distorted octahedral configuration with two chloro ligands in cis position. The tin atom is also at a pseudo two-fold axis of inversion for both the ligand anions and the two cis-chloro ligands. The orange compound crystallizes in the triclinic space group P 1 with unit cell dimensions, a = 8.741(3) Å, b = 12.325(7) Å, c = 13.922(7) Å; = 71.59(4), = 79.39(3), = 75.18(4); Z = 2 and Dx = 1.575 g cm-3. The important bond distances in the chelate ring are Sn-O [2.041 to 2.103 Å], Sn-Cl [2.347 to 2.351 Å], C-O [1.261 to 1.289 Å] and C-C [1.401 Å] the bond angles are O-Sn-O 82.6 to 87.7° and Cl-Sn-Cl 97.59°. The UV, IR, 1H NMR and 119Sn Mössbauer spectral data of the compound are reported and discussed.