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Eingeladener Vortrag
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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.
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.
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.
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 Mössbauer 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 PtFe 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.
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.
Metallosupramolecular coordination polyelectrolytes (MEPEs) based on rigid and flexible ditopic bis-terpyridine ligands and Fe(II) ions are investigated by Mössbauer spectroscopy. We demonstrate the influence of mechanical stress induced by grinding on the structure of MEPE as well as the ability of MEPE to self-repair through recrystallisation.
Single-crystals of chromium doped with 10 16 119Sn ions per cm2 and energies ranging between 45 and 190 keV were investigated with conversion electron Mössbauer spectroscopy (CEMS), Auger electron spectroscopy (AES), grazing angle X-ray diffraction (GAXRD), and scanning electron microscopy (SEM). The Mössbauer spectra were found to be significantly different than those of the bulk. Both the maximum and the average hf. field values were higher by a factor of ˜3 than the corresponding quantities for the bulk. The overall shape of the spectra is also different. GAXRD study has revealed that the near-surface zone of the investigated samples has a nanocrystalline structure with the average size of grains ranging between ˜20 and ˜40 nm. The latter seems to be the main reason for the observed enhancement of the spin-density and its distortion.
Polyvalent Ions - Their Behaviour in the Glass Melt and their Influence on Glass Crystallisation
(1998)
The investigation of iron-doped AlO(OH)/Al2O3 systems revealed that the combined employment of Mössbauer 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.
Systematic 119mSn-Mössbauer spectroscopy studies of three different types of five and six coordinated molybdenum and tungsten stannylidyne complexes are presented. The measured isomer shifts (IS) range from 2.38 to 2.50 mm/s and the quadrupole splittings (QS) from 1.8 to 2.8 mm/s. The values are dependent on the metal centre, the ligand sphere and the charge of the complexes. The influence of the neighbouring metal atoms (Mo, W) and their coordination sphere on the electron density at the tin atom is observed and will be discussed.
The mainstream magnetic iron oxide particles used as contrast media for magnetic resonance (MR) imaging are composed of a magnetic iron oxide core surrounded by a dextran or carboxydextran coat. The core size ranges from 2 nm to less than 10 nm, and the hydrodynamic diameter ranges from 20 nm to about 120 nm. The coat prevents aggregation and sedimentation of the particles in aqueous solutions, achieves high biological tolerance, and prevents toxic side effects.
Two kinds of particles are considered: (i) large particles (>30 nm), called superparamagnetic iron oxide particles (SPIOs) for liver imaging; (ii) smaller particles (<30 nm hydrodynamic diameter), called ultrasmall SPIOs (USPIOs), e.g. for MR angiography.
To characterize the particles, Mössbauer spectra are presented for the two particle ensembles. These spectra allow insight into the magnetic coupling, the valency of the iron ions and a rough estimate of the core size to be deduced. On the basis of the concentration dependence of the MR signal intensities, two applications are discussed together with two representative clinical examples.
Spin transition in heptanuclear star-shaped iron(III)-antimony(V) NCS- and CN-bridged compounds
(2009)
The precursor [FeIII(L)Cl] (LH2 = N,N'-bis(2'-hydroxy-benzyliden)-1,6-diamino-3-azahexane) has been prepared and Mössbauer spectroscopy assigned a high-spin (S = 5/2) state at room temperature. The precursor is combined with the bridging units [SbV(X)6]- (X = CN-, NCS-) to yield star-shaped heptanuclear clusters [(LFeIII-X)6SbV]Cl5. The star-shaped compounds are in general high-spin systems at room temperature. On cooling to 20 K some of the iron(III) centers switch to the low-spin state as indicated by Mössbauer spectroscopy, i.e. multiple electronic transitions. While the cyano-bridged complex performs a multiple spin transition the thiocyanate-compound shows no significant population at both temperatures.
The precursor [FeIII(L)Cl] (LH<sub2 = N,N'-bis(2'-hydroxy-benzyliden)-1,6-diamino-3-N-hexane is a high-spin (S = 5/2) complex. This precursor is combined with the bridging units [SnIV(X)4] (X = CN-, NCS-) to yield star-shaped pentanuclear clusters, [(LFeIII-X)4Sn]Cl4. For X = CN- the 57Fe-Mössbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state, while the 119mSn-Mössbauer data indicate a valence tautomerism between Sn(IV) and Sn(II). Changing the bridging unit from X = CN- to X = NCS- turns the switchability off.
The fate of doped iron species during various mechanically and thermally initiated redox reactions and aggregation processes in crystalline and amorphous AlO(OH) or Al2O3 matrices was investigated. The amorphization of the matrix was performed by chemical (i.e., via sol-gel processes) or mechanochemical treatment (high-energy ball milling). Thermal analysis, coupled with mass spectrometry (TA-MS), Mössbauer spectroscopy, and electron spin resonance (ESR), was used. The TA under various gas atmospheres allowed preparing samples under a controlled temperature regime, together with a controlled gas influence. Both the effect of mechanical activation and the influence of the iron doping could be followed macroscopically via the down-shift of the peak temperature of the corundum formation. The ESR data characterize the Fe3+ ions and their interaction with the magnetic surrounding based on the fine structure parameters. The Mössbauer data allowed the characterization of the Fe(0), Fe2+, and Fe3+ species, together with providing information about their coordinative surrounding. Both methods provided general complementary spectroscopical information.
Unexpectedly, (FeOx)n and (FexAl1-x)2O3 aggregates could also be detected in the range of low Fe concentrations. It was demonstrated that even in the low-level doped systems [(FexAl1-x)2O3 with x ≥ 0.01], all the essential spectroscopic phenomena occur. At higher Fe concentrations, they were discovered to be caused by magnetic and spin exchange interactions as well as by solid-state reactions during and after the mechanical activation.
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 Mössbauer 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.
Fe-ZSM-5 Catalysts for the Selective Reduction of NO by Isobutane - The Problem of the Active Sites
(2002)
Relations between the structure of FeZSM-5 catalysts prepared by interaction of FeCl3 with HZSM-5 and their catalytic behavior in the SCR of NO by isobutane were investigated by combining results of catalytic studies (1000 ppm NO, 1000 ppm isobutane, and 2% O2 in He, 30,000 h-1) and of physicochemical characterization (XRD, EXAFS, Mössbauer spectroscopy, TPR, IR, XPS). By variation of the preparation conditions (method of FeCl3 introductionchemical vapor deposition or solid-state ion exchange, washing intensity, calcination regime) and of the matrix (HZSM-5 with normal and high defect density), FeZSM-5 materials with strongly varying properties (aggregation degree of the Fe phase, acidity) were obtained. Significant discrepancies between conclusions derived from EXAFS, TPR, and Mössbauer spectroscopy were ascribed to a preference of Mössbauer spectroscopy for the detection of aggregated phases and a high defectivity of Fe oxide clusters formed upon calcination. The critical step for the preparation of a highly disperse Fe phase is extensive washing after Fe introduction. The catalytic behavior of overexchanged FeZSM-5 materials prepared by interaction of FeCl3 with HZSM-5 of normal defect density was not influenced by aggregation of a significant part of the Fe phase. The comparison of their catalytic properties with those of a Fe2O3/HZSM-5 mechanical mixture and of catalysts prepared by aqueous ion exchange or by CVD of FeCl3 into HZSM-5 of high defect density implies that the particular activity of overexchanged FeZSM-5 arises from minority sites. In these, the Fe ions are probably isolated. Other Fe sites of low nuclearity appear to add to the activity. The poor SCR performance (at a given ability for isobutane activation) of FeZSM-5 prepared with a defective ZSM-5 matrix may indicate that the Fe sites which provi de the particular activity of overexchanged FeZSM-5 require the cooperation of acidic sites.
Characterization of the microstructure of high-chromium cast irons using Mössbauer spectroscopy
(2001)
The finish grinding process for cement materials uses ball mills with differently sized grinding balls. Because the grinding takes place through the impact and friction of the balls, balls with a high wear resistance are desirable and the materials of choice are the high-chromium white cast irons. This article examines the behavior of these cast irons when subjected to various heat treatments. The emphasis is on the dependence of the microstructure properties on the chemical composition of the alloys and the heat treatment parameters. The content of retained austenite and that of carbon in the martensite phase were determined by the use of Mössbauer spectroscopy. The results verify that a higher proportion of retained austenite with low carbon content and a martensite with higher hardness produce a material with good fracture toughness and resistance to abrasive wear.
Redox reactions of K3[Fe(CN)6] during mechanochemically stimulated phase transitions of AlOOH
(2011)
Thermally induced redox reactions of K3[Fe(CN)6] (1) were investigated for a broad temperature range by thermal methods and structure analytical methods (ESR and Mößbauer spectroscopy, X-ray Powder diffraction and XANES). Based on the influence of the mechanically activated and transforming matrices 2 and 3, redox processes can be tuned to form doped Al2O3 systems which contain either isolated Fe3+ centres or redox active phases and precursors like (Al1-xFex)2O3 (4), (Al3-xFex)O4 (5), Fe3O4, Fe2O3 and Fe0. The phase Fe3C and the chemically reactive C-species were detected during the reaction of 1. The final composition of the doped products of α-Al2O3 is mainly influenced by the chemical nature of the Fe doping component, the applied temperature and time regime, and the composition of the gas phase (N2, N2/O2 or N2/H2). From the solid state chemistry point of view it is interesting that the transforming matrix (2 and 3) possesses both oxidative and protective properties and that the incorporation of the Fe species can be performed systematically.
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.
Evidence is provided that the tridymite component observed in the X-ray diffraction patterns of some sewage sludge ashes (SSAs) should not be interpreted as the tridymite modification of SiO2 but as the tridymite form of AlPO4. This proof is based on a combined X-ray Powder Diffraction (XRD), X-ray fluorescence (XRF) and Mossbauer spectroscopy investigation of two SSAs produced at two fluidized bed incineration facilities, located in different municipalities and operated differently. The structural and chemical characterization was carried out on the 'as received' SSA samples as well as on the residues of these two SSAs pretreated by leaching in citric acid. In addition, direct proof is presented that the tridymite form of AlPO4 does crystallize from X-ray amorphous precursors under conditions that mimic the huge heating rate and short retention time (just seconds at T ≈ 850 °C) typical for fluidized bed incinerators.
Dendrimers of various generations were synthesized by the divergent method. Starting from various amine cores (G0a, G0b, G0c) the generations were built by reaction of the amine with acrylnitrile followed by hydrogenation with DIBAL-H. Treatment with salicylaldehyde creates a fivefold coordination sphere for iron in the molecular periphery. The resulting multinuclear coordination compounds are investigated by Mossbauer spectroscopy.
The syntheses, crystal structures, and physical properties of [HFe19O14(OEt)30] and {Fe11(OEt)24}1 are reported. [HFe19O14(OEt)30] has an octahedral shape. Its core with a central Fe metal ion surrounded by six m6-oxo ligands is arranged in the rock salt structure. {Fe11(OEt)24}1 is a mixedvalence coordination polymer in which FeIII metal ions form three 3D interpenetrating (10,3)-b nets. The arrangement of the FeIII ions can also be compared to that of Si ions in a-ThSi2. Thus, the described structures are at the interface between molecular and solid-state chemistry.
Sewage sludge and sewage sludge ashes (SSA) are produced in huge amounts at municipal waste water treatment plants (WWTP) all around the world and have become an issue for many urbanized areas. To deal with this unceasing mass flow in an ecologically and economically responsible way a comprehensive chemical and structural characterization of all types of SSA is needed. X-ray powder diffraction (XRD) is one of the most promising analytical methods for this task. Although, there has been ample chemical evidence showing that many SSA contain aluminium phosphate as a major component up to now no aluminium phosphate or aluminium-rich mixed phosphate phase has been reported to be identified by XRD in a SSA produced at a mono-incineration facility. The outcome of the present com-bined XRD and Mossbauer spectroscopy investigation provides comprehensive evidence closing this gap for the first time.
The precursor [FeIII(L)Cl] (LH2 = N,N'-bis(2'-hydroxy-3'-X-benzyliden)-1,6-diamino-3-N-hexane) is a high-spin (S = 5/2) complex (with X = -CH3, -O-CH3). This precursor is combined with the bridging unit [SnIV(CN)4] to yield star-shaped pentanuclear clusters, [(L-X-FeIII)4Sn(CN)4]Cl4 57Fe-Mössbauer, 119mSn-Mössbauer, and ESR spectroscopy are used to study our samples. For X = -CH3 the 57Fe-Mössbauer data show a multiple spin transition between iron(III) in the high-spin and low-spin state. Changing the functional group from X = -CH3 to X = -O-CH3 turns the switchability off.