Michael Menzel

Tin promoted palladium catalysts for nitrate removal from drinking water

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-Mossbauer 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 palladium–tin 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.

The solid-state architecture of a metallosupramolecular polyelectrolyte

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.

Magnetic properties and oxidation state of iron in bimetallic Pt-Fe/KL zeolite catalysts

In view of an understanding of catalytic efficiency the electronic and magnetic state of iron in Fe/KL and the influence of Pt on these properties in Pt-Fe/KL were investigated by superconducting quantum interference device (SQUID) magnetization measurements and Mossbauer spectroscopy. After calcination in air, iron is present only as Fe3+ ions in both samples, mainly in a paramagnetic state. There is also a small antiferromagnetic contribution, probably due to iron oxide and hydroxide particles which precipitate on the outer surface of the zeolite crystallites during preparation. After reduction in H2, the behavior of both samples is predominantly superparamagnetic, but the presence of Pt increases both the saturation magnetization and the size of the residual hysteresis loop. At the same there remains a pronounced paramagnetic contribution which appears to be even slightly higher than before reduction. The interpretation is that alloy particles of metallic Pt–Fe are formed on the outer surface. Since small clusters inside the zeolite crystallites are most active for catalysis the alloy formation seems to be not of relevance for an enhancement of sulfur resistance. It was also shown that during reduction a fraction of Fe2+ is formed. The coordination of the Fe2+ ions is clearly influenced by Pt and it seems very likely that Fe2+ ions are in close contact with Pt clusters. This interaction is probably the origin of the enhanced sulfur resistance and catalytic activity in the reforming reactions.

Synthesis, Spectroscopic, and X-Ray Diffraction Studies ofcis-Dichlorobis(4-propanoyl-2,4-dihydro-5-methyl-2-phenyl3 H-pyrazol-3-onato) Tin(IV)

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) A, b = 12.325(7) A, c = 13.922(7) A; = 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 A], Sn-Cl [2.347 to 2.351 A], C-O [1.261 to 1.289 A] and C-C [1.401 A] 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 Mossbauer spectral data of the compound are reported and discussed.

Investigation of PdSn-catalysts for nitrate removal in drinking water processing

PdSn catalysts prepared by various methods and used for nitrate reduction were investigated by means of in situ 119mSn Mössbauer spectroscopy. Characterization by 119mSn Mössbauer spectroscopy revealed significant differences concerning the modification of the palladium particles supported on alumina. The controlled surface reaction preparation method (CSR) leads to formation of PdSn alloys with different tin contents besides small amounts of Sn(II) species and unalloyed metallic Sn. On the other hand the impregnation method leads to a small amount of PdSn alloys and higher contents of Sn(II) species. Sn(IV) species were found in both kinds of catalysts. The CSR prepared PdSn catalysts showed an improved activity and selectivity compared to the catalysts obtained by the impregnation method.

[Fe19 ] "Super-Lindqvist" Aggregate and Large 3D Interpenetrating Coordination Polymer from Solvothermal Reactions of [Fe2 (OtBu)6 ] with Ethanol.

The syntheses, crystal structures, and physical properties of [HFe19 O14 (OEt)30 ] and {Fe11 (OEt)24 }∞ are reported. [HFe19 O14 (OEt)30 ] has an octahedral shape. Its core with a central Fe metal ion surrounded by six μ6 -oxo ligands is arranged in the rock salt structure. {Fe11 (OEt)24 }∞ is a mixed-valence coordination polymer in which Fe(III) metal ions form three 3D interpenetrating (10,3)-b nets. The arrangement of the Fe(III) ions can also be compared to that of Si ions in α-ThSi2 . Thus, the described structures are at the interface between molecular and solid-state chemistry.

Precision in Mössbauer Spectroscopy

In this paper the factors which are responsible for precision and reliability of the experimental data are discussed. The detectors of different types are compared with respect to the precision of the final results. It is shown that the use of resonance detectors gives the best results in most cases of the Sn-119m Mossbauer spectroscopy. The estimation of spectral line distortion caused by a short distance between source and detector is presented. Different procedures of velocity scale calibration are discussed. It has to be underlined that Kuprijanov’s method of the velocity scale calibration gives the most reliable and fast results.

Competing redox reactions in Fe-containing AlO(OH) and Al2O3 matrices: A combined investigation by Mössbauer, ESR spectroscopy and thermal analysis

The investigation of iron-doped AlO(OH)/Al2O3 systems revealed that the combined employment of Mossbauer and ESR spectroscopies together with thermal analysis yields meaningful data with complementary information. This mutual complementarity is based on the coexistence of Fe point defects with the corresponding aggregated FeOx species which has been observed even for very low Fe concentrations. Competing redox processes between the dopant, the AlOx matrix, and the gas atmosphere during the thermal treatment enable the generation of solid phases exhibiting specific chemical properties. The entire reaction process is influenced by a specific mechanical and thermal pre-treatment that affects predominantly oxydative processes in the matrix. A protecting influence of the matrix preventing further reductive attack of the Fe3+ Fe2+ ions by hydrogen has been established.

Laboratory Intercomparison on the Determination of the Fe(II)/Fe(III) Ratio in Glass Using Mössbauer Spectroscopy

The Mossbauer community all over the world was given the opportunity to determine the Fe(II)/Fe(III) ratio in 4 glass samples of different total iron content, to classify themselves with respect to their measurement technique and especially to their kind of evaluation.

Baseline investigation in transmission Mössbauer spectroscopy using resonance detectors

It was recognized, that the baseline in transmission Mossbauer spectroscopy using resonance detectors reveals a specific distortion. This distortion was investigated from both the experimental and theoretical point of view. It was shown, that this specific distortion caused by an energy shift of the gamma-quanta that were Rayleigh- scattered from the moving sample.