Mossbauer absorption spectroscopy

Mossbauer Absorption Spectroscopy (MAS) Mossbauer Emission Spectroscopy (MES)... 

A Mossbauer spectrometer consists of a radioactive Co source on a transducer that continuously scans the desired velocity range, an absorber consisting of the catalyst and a detector to measure the intensity of the gamma radiation transmitted by the absorber as a function of the source velocity. This is the common mode of operation, called Mossbauer absorption spectroscopy, sometimes abbreviated as MAS. It is also possible to fix the Co containing source and move a single-line Fe absorber, in order to investigate Co-containing catalysts. This technique, called Mossbauer emission spectroscopy (MES), has successfully been applied to study Co-Mo hydrodesulphurization catalysts [42]. 

Mossbauer Absorption Spectroscopy. Spectra were acquired at room temperature in a constant acceleration spectrometer using a Co in Rh source. Isomer shifts are relative to the NBS standard sodium nitroprusside. Magnetic hyperfine fields were calibrated with the 515 kOe field of a-FcjO, at RT. Mossbauer parameters were determined by fitting the collected spectra with reference sub-spectra consisting of Lorentzian-shaped lines using a non-linear iterative minimization routine. 

In conventional Mossbauer spectroscopy one uses a single-line source, e.g. Co embedded in a rhodium matrix in the case of Fe spectroscopy, and the iron containing material under study as absorber. This technique is termed Mossbauer Absorption Spectroscopy (MAS) in order to distinguish it from the so-called source experiment, also known as Mossbauer Emission Spectroscopy (MES). In a MES... 

Table 1.38 summarises the main features of Mossbauer spectroscopy. The great advantage of Mossbauer spectroscopy for in-polymer additive analysis is that it provides in situ information. An economic advantage is that the technique is relatively inexpensive in comparison to electron microscopy or XPS. The technique is limited to those isotopes that exhibit the Mossbauer effect. The detection limit is 10 atoms of the nuclear isotope studied. Through the Mossbauer effect in iron, it is possible to obtain information on the state of cobalt. Whereas in Mossbauer absorption spectroscopy (MAS) a single-line source is moved and... 

Mossbauer effect spectroscopy, MES, Is based on the ability of certain nuclei to undergo recoilless emission and absorption ofY rays (16). The energy and multiplicity of the ground and excited states of a given nucleus are modified by the chemical environment. It Is thus most often necessary to compensate for the differences In... 

Mossbauer spectroscopy with started only in 1965, when Harris et al. [322] measured the Mossbauer absorption spectra of the 99 keV transition of Pt in platinum metal as a function of temperature (between 20 and 100 K) and of absorber thickness and derived the temperature dependence of the Debye-Waller factor. 

The verification of the presence of hydrogen in the film has proved more controversial, primarily because many of the structural investigations have been carried out after the film has been dried in vacuo. An example of the problems here is the fact that electron diffraction, which has to be carried out in vacuo, reveals a relatively well-crystallised spinel lattice whose origin may be the comparatively high sample heating encountered in the electron beam. Moreover, the use of in situ techniques, such as Mossbauer and X-ray absorption spectroscopy, clearly reveals marked differences between the spectra of the films in situ and the spectra of the same films ex situ as well as the spectra of y-Fe203 and y-FeOOH standards. These differences are most naturally ascribed to hydration of the spinel forms. 

Mossbauer Measurements. Co-Mo catalysts cannot be studied directly in absorption experiments since neither cobalt nor molybdenum has suitable Mossbauer isotopes. However, by doping with 57Co the catalysts can be studied by carrying out Mossbauer emission spectroscopy (MES) experiments. In this case information about the cobalt atoms is obtained by studying the 57Fe atoms produced by the decay of 57Co. The possibilities and limitations on the use of the MES technique for the study of Co-Mo catalysts have recently been discussed (8., 25.). 

Recently, however, considerable doubt has been cast on these conclusions. In the case of the putative Mg/Al/Sn - CO3, Mg/Al/Zr - CO3 and Co/Al/Sn - CO3 materials it has been unambiguously shown by X-ray absorption spectroscopy (XAS) and Mossbauer spectroscopy that the tetravalent cations are segregated from the LDH structure and form amorphous oxide-hke particles [69]. It was further demonstrated that the increased values of Uo previously attributed to the introduction of the large cations... 

Thanks to the extensive literature on Aujj and the related smaller gold cluster compounds, plus some new results and reanalysis of older results to be presented here, it is now possible to paint a fairly consistent physical picture of the AU55 cluster system. To this end, the results of several microscopic techniques, such as Extended X-ray Absorption Fine Structure (EXAFS) [39,40,41], Mossbauer Effect Spectroscopy (MES) [24, 25, 42,43,44,45,46], Secondary Ion Mass Spectrometry (SIMS) [35, 36], Photoemission Spectroscopy (XPS and UPS) [47,48,49], nuclear magnetic resonance (NMR) [29, 50, 51], and electron spin resonance (ESR) [17, 52, 53, 54] will be combined with the results of several macroscopic techniques, such as Specific Heat (Cv) [25, 54, 55, 56,49], Differential Scanning Calorimetry (DSC) [57], Thermo-gravimetric Analysis (TGA) [58], UV-visible absorption spectroscopy [40, 57,17, 59, 60], AC and DC Electrical Conductivity [29,61,62, 63,30] and Magnetic Susceptibility [64, 53]. This is the first metal cluster system that has been subjected to such a comprehensive examination. 

However, spectroscopic studies of activated BLM indicate that it is not an Fev=0 species. It exhibits an S - 1/2 EPR spectrum with g values at 2.26, 2.17, and 1.94 [15], which is typical of a low-spin Fe111 center. This low-spin Fem designation is corroborated by Mossbauer and x-ray absorption spectroscopy [16,19], Furthermore, EXAFS studies on activated BLM show no evidence for a short Fe—0 distance, which would be expected for an iron-oxo moiety [19], These spectroscopic results suggest that activated BLM is a low-spin iron(III) peroxide complex, so the two oxidizing equivalents needed for the oxidation chemistry would be localized on the dioxygen moiety, instead of on the metal center. This Fe(III)BLM—OOH formulation has been recently confirmed by electrospray ionization mass spectrometry [20] and is supported by the characterization of related synthetic low-spin iron(III) peroxide species, e.g., [Fe(pma)02]+ [21] and [Fe(N4py)OOH]2+ [22], The question then arises whether the peroxide intermediate is itself the oxidant in these reactions or the precursor to a short-lived iron-oxo species that effects the cytochrome P-450-like transformations. This remains an open question and the subject of continuing interest. 

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