Mössbauer spectroscopy in catalysis

Application of in situ Mössbauer spectroscopy for studying catalysts and catalytic processes is discussed. Examples are presented to illustrate the potentials of the method by describing studies on supported heterogeneous catalysts performed with ¹¹⁹Sn and ⁵⁷Fe spectroscopies in cases with certain metals and alloys, oxides and porous substances. The results are interpreted in comparison to the catalytic performance.     

67Zn Mössbauer spectroscopy

The 93.31-keV Mössbauer resonance in⁶⁷Zn is used to determine tiny changes of the transition energy. We first report on a gravitational redshift (GRS) experiment with⁶⁷GaZnO single crystal source and⁶⁷ZnO powder as absorber. The results on the GRS show that solid state effects which are difficult to control experimentally, in particular the extreme sensitivity of the electric field gradient tensor (efg) in⁶⁷ZnO to small external pressure, finally limit the accuracy in determining the GRS. The resonance has been further employed to investigate solid state properties of⁶⁷ZnO with high precision. At large pressures⁶⁷ZnO exhibits a phase transition from hep (wurtzite) to fcc (NaCl) structure. The changes of the efg and of the s-electron density θ(0) at the⁶⁷Zn nucleus with reduced unit cell volume show that covalency of the Zn-O bond plays and essential role. We have performed self-consistent Hartree-Pock cluster calculations to describe the experimental changes of θ(0) in detail.     

Mössbauer spectroscopy in molecular magnetism

The aim of this paper is to highlight some selected research activities on molecular magnetic materials using Mössbauer spectroscopy as a technique carried out in our laboratory in recent years. The first part of the present article is devoted to the studies of the various magnetic interactions, metal-to-metal electron-transfer phenomenon, glass transition occurring in molecular magnetic materials, whereas the second part deals with the iron(II) high spin (S = 2)–low spin (S = 0) transition phenomenon occurring in some isoxazole ligand based iron(II) compounds as examples with unusually complicated spin transition behaviour. Also, an example of a dinuclear a spin crossover compound of iron(II) is described, where Mössbauer spectroscopy has most convincingly unraveled the mechanism of the spin transition process. Finally, an example from our most recent studies of spin crossover materials exhibiting both thermal spin crossover and liquid crystalline properties in the same temperature interval near room temperature will be presented.     

Mössbauer spectroscopy of zirconium alloys

Mössbauer investigations of zirconium alloys were examined. Data about the chemical state of iron atoms in the zirconium alloys of different composition has been provided. Mössbauer spectroscopy revealed that small quantities of iron in binary zirconium alloy are in the solid solution α-Zr (up to 0.02 wt.%). Different iron atoms concentration and thermo-mechanical treatments may lead to formation the intermetallic compounds Zr₃Fe, Zr₂Fe, ZrFe₂. Adding tin atoms does not affect the formation and shape of Mössbauer spectra of these compounds. Adding Cr and Nb atoms makes significant changes in the shape of Mössbauer spectra and leads to the formation of complex intermetallic compounds. Adding Cu and W atoms, the shape of the binary alloys spectra (Zr-Fe) remains unchanged, but a change in the temperature dependence behavior of the spectral parameters occurs and also, changes to the properties of the alloys.     

Mössbauer spectroscopy with actinide elements

Although formally equivalent to the lanthanide (4f) elements, the light actinides show a much more varied behaviour due to the larger spatial extent and ionizability of the 5f electrons. The application of Mössbauer spectroscopy for the determination of electronic properties of the actinides is outlined. Emphasis is put on high pressure Mössbauer experiments using the 60 keV transition in²³⁷Np to study questions of delocalization of 5f electrons.Work performed under the auspices of the Bundesministerium für Forschung und Technologie, Federal Republic of Germany.     

Mössbauer spectroscopy in physical metallurgy

In this anniversary contribution the natural and intimate match making which occurs between the two star performers-⁵⁷Fe in Mössbauer spectroscopy and iron in physical metallurgy—is described by selecting typical examples reflecting the author's interest: phases, f.c.c. -Fe, defects, diffusion and amorphous metals.     

Fast detectors for Mössbauer spectroscopy

The methods to increase the productivity (statistical quality) of Mössbauer measurements have been considered. Some fast detectors for gamma- and secondary radiation have been described. These detectors allow in many cases to essentially reduce the time for the Mössbauer spectra accumulation with a given productivity.     

Mössbauer spectroscopy of 151 europium dicarboxylates

We have previously reported the stability of europium oxalate compared to ammonium europium bis-salen and europium benzoate. We now extend the dicoarboxylic acid chain of the oxalate by introducing additional-CH₂-groups in the dicarboxylate ligands by using malonate, succinate, glutarate and adipate. Additionally, we have examined the effect of alterations in the succinate dianion by introducing functional groups such as [C = C]in the case of the maleide and-OH group in the case of the malide. This study is an attempt to further characterize these compounds. Infrared spectra were used to characterize bridging and chelating dicarboxylates while Mössbauer spectroscopy measurements were used to gain better insight into the structure of heterocyclic “cages” containing two Eu^3?+? ions and two dianions.     

Digital pulse processing in Mössbauer spectroscopy

In this work we present some advances towards full digitization of the detection subsystem of a Mössbauer transmission spectrometer. We show how, using adequate instrumentation, preamplifier output of a proportional counter can be digitized with no deterioration in spectrum quality, avoiding the need of a shaping amplifier. A pipelined architecture is proposed for a digital processor, which constitutes a versatile platform for the development of pulse processing techniques. Requirements for minimization of the analog processing are considered and experimental results are presented.     

Practical aspects of Mössbauer spectroscopy instrumentation

The setting up and updating of a Mössbauer laboratory imply the acquisition and assembling of different units. Guidelines concerning either the construction or the acquisition of the various parts which compose a Mössbauer spectrometer are given in this paper.     

Laser-produced iron nitrides seen by Mössbauer spectroscopy

Mössbauer spectroscopy is a very powerful tool to investigate technological processes performed mainly at the surface of materials. Nitriding of metals and steel is well established in surface engineering, and gas nitriding is used most frequently. Laser nitriding, i.e. the nitrogen take-up from the ambient gas upon irradiation of a steel surface with short laser pulses, is presented in its application to iron, stainless steel and plain carbon steels. It will be demonstrated how Mössbauer spectroscopy in combination with complementary methods (Rutherford backscattering spectroscopy, Resonant nuclear reaction analysis, Nanoindentation) can help to reveal basic mechanisms in these processes.     

Development of 125Te synchrotron-radiation-based Mössbauer spectroscopy

The Mössbauer spectra of the 35.49 keV excited state of ¹²⁵Te were observed in the energy domain using synchrotron radiation for the first time. The obtained isomer shifts and Debye temperature agree with previous experiments. These results show that this method will be applicable to various compounds.     

Characterization of magnetic nano-fluids via Mössbauer spectroscopy

The laser pyrolysis became a useful tool, providing various ways, in production of nano materials. The iron Mössbauer spectroscopy is one very accurate method in evidencing the physical properties and related processes in the nano scale compounds. The effect of pressure, laser spot area and induced combustion, of gas mixture and laser power on the phase composition and inside particle distribution, grain size as well as the related phenomena were investigated by temperature dependent Mössbauer spectroscopy. A selection of most relevant properties is presented and discussed in details.     

Tin Mössbauer spectroscopy of tin-rich iridium-tin alloys

Ir₅Sn₇, Ir₃Sn₇ and newly obtained IrSn₄ /4/ exhibit complex Mössbauer spectra. The positions of the individual lines range from 0.82 to 3.0 mm/s and the average isomer shift \(\overline {IS} \) derived for each compound of Sn atomic percentage x follows the relationship: \(\overline {IS} = 0.60 + 0.0194 x\) . Rather large quadrupole splittings are obtained. The f factors are about 0.20 at 295 K and 0.37 at 78 K, from which Debye temperatures of 200 to 300 K have been calculated.     

Mössbauer spectroscopy of lanthanum and holmium ferrites

PrRh₂Si₂ is highly anisotropic Ising-type antiferromagnetic system. The ordering temperature (T _N~ 68 K) of PrRh₂Si₂ is exceptionally high on the de-Gennes scale in the family of RRh₂Si₂ (R = rare earths). The reason for this anomalous behaviour is not clear. It is believed that the presence of uniaxial anisotropy assists in enhancing the T _N. The Mössbauer study was performed on a 10% Fe-doped PrRh₂Si₂ sample to understand the magnetic coupling between different sites of PrRh₂Si₂. The Mössbauer spectra together with the magnetic susceptibility data suggest that the magnetic coupling in PrRh₂Si₂ is provided mainly by the RKKY interaction between Pr-moments.     

Mössbauer spectroscopy study of interfaces for spintronics

The submonolayer sensitivity and element-specificity of conversion electron Mössbauer spectroscopy, combined with the use of ⁵⁷Fe enriched tracer layers, enable to carefully investigate thin films and interfaces at the atomic-scale. This paper reports on the main achievements we obtained so far in the study of structural, chemical, and magnetic properties of a variety of interfaces between oxides and Fe-based films having potential interest in the field of spintronics.     

Characterisation of synthetic trioctahedral micas by Mössbauer spectroscopy

Trioctahedral potassium micas |K}[M₃]〈T₄〉O₁₀(OH)₂ have been synthesized by hydrothermal techniques with various cationic substitutions in the octahedral and the tetrahedral sheet. Taking annite |K}[Fe ₃ ²⁺ ]〈AlSi₃〉O₁₀(OH)₂ as the reference mineral, [Fe²] was replaced by [Mg²] and [Ni²], 〈Al³⁺〉 by 〈Fe³⁺〉 and finally [Fe²⁺] + 〈Si⁴⁺〉 by [Al³⁺] + 〈Al³⁺〉. Mössbauer spectra were evaluated in terms of quadrupole splitting distributions (QSDs) using three generalized sites for 〈Fe³⁺〉, [Fe³⁺] and [Fe²]. Annites, nominally free of 〈Fe³⁺〉, show a lower limit of [Fe³⁺]/Fe _tot of 0.10, which stabilizes the structure. The ferrous iron, [Fe²], QSD consists of two main components. In some of the solid solution series, there is strong experimental evidence for a third ferrous component, particularly at higher [Al³⁺] contents. This third component is centered at low quadrupole splittings and may be assigned to a defect [Fe²] site, forming 1:2 structures with two neighbouring trivalent octahedral cations. For charge compensation one OH^? is replaced by O^2? for each [M³⁺] cation. The ferrous QSDs vary systematically with chemical composition. Compared to those of annite, the QSD parameters (mean quadrupole splitting 〈QS〉 and quadrupole splitting with maximum probability, QS _peak ) are shifted towards higher values with increasing [Mg²] and [Ni²] contents, and decrease slightly with increasing content of trivalent cations. These trends can be interpreted in terms of changes in the local environment around the Fe probe nucleus, i.e., in terms of decreasing or increasing distortions from the ideal octahedral configurations.     

Mössbauer spectroscopy in determining the gas molecular state

A possibility of conversion electron Mössbauer spectroscopy for determining the gas molecular state is shown. For acceleration of gas interaction with active surface the thin iron layer enriched with ⁵⁷Fe was applied on aluminum foil and gas discharge is used.     

Mössbauer spectroscopy on Mars: goethite in the Columbia Hills at Gusev crater

In January 2004 the USA space agency NASA landed two rovers on the surface of Mars, both carrying the Mainz Mössbauer spectrometer MIMOS II. The instrument on the Mars-Exploration-Rover (MER) Spirit analyzed soils and rocks on the plains and in the Columbia Hills of Gusev crater landing site on Mars. The surface material in the plains have an olivine basaltic signature [1, 5] suggesting physical rather than chemical weathering processes present in the plains. The Mössbauer signature for the Columbia Hills surface material is very different ranging from nearly unaltered material to highly altered material. Some of the rocks, in particular a rock named Clovis, contain a significant amount of the Fe oxyhydroxide goethite, α-FeOOH, which is mineralogical evidence for aqueous processes because it is formed only under aqueous conditions. In this paper we describe the analysis of these data using hyperfine field distributions (HFD) and discuss the results in comparison to terrestrial analogues.