Cobalt, Mossbauer

Mossbauer spectroscopy is one of the techniques that is relatively little used in catalysis. Nevertheless, it has yielded very useful information on a number of important catalysts, such as the iron catalyst for Fischer-Tropsch and ammonia synthesis, and the cobalt-molybdenum catalyst for hydrodesulfurization reactions. The technique is limited to those elements that exhibit the Mossbauer effect. Iron, tin, iridium, ruthenium, antimony, platinum and gold are the ones relevant for catalysis. Through the Mossbauer effect in iron, one can also obtain information on the state of cobalt. Mossbauer spectroscopy provides valuable information on oxidation states, magnetic fields, lattice symmetry and lattice vibrations. Several books on Mossbauer spectroscopy [1-3] and reviews on the application of the technique on catalysts [4—8] are available. 

A number of ferrites have been subjected to shock modification and studied with x-ray diffraction as well as static magnetization and Mossbauer spectroscopy [87V01], Studies were carried out on cobalt, nickel, and copper ferrites as well as magnetite (iron ferrite). 

Electrobalances suitable for thermogravimetry are readily adapted for measurements of magnetic susceptibility [333—336] by the Faraday method, with or without variable temperature [337] and data processing facilities [338]. This approach has been particularly valuable in determinations of the changes in oxidation states which occur during the decompositions of iron, cobalt and chromium oxides and hydroxides [339] and during the formation of ferrites [340]. The method requires higher concentrations of ions than those needed in Mossbauer spectroscopy, but the apparatus, techniques and interpretation of observations are often simpler. 

Some of the transition metal macrocycles adsorbed on electrode surfaces are of special Interest because of their high catalytic activity for dloxygen reduction. The Interaction of the adsorbed macrocycles with the substrate and their orientation are of Importance In understanding the factors controlling their catalytic activity. In situ spectroscopic techniques which have been used to examine these electrocatalytlc layers Include visible reflectance spectroscopy surface enhanced and resonant Raman and Mossbauer effect spectroscopy. This paper Is focused principally on the cobalt and Iron phthalocyanlnes on silver and carbon electrode substrates. 

Of special Interest as O2 reduction electrocatalysts are the transition metal macrocycles In the form of layers adsorptlvely attached, chemically bonded or simply physically deposited on an electrode substrate Some of these complexes catalyze the 4-electron reduction of O2 to H2O or 0H while others catalyze principally the 2-electron reduction to the peroxide and/or the peroxide elimination reactions. Various situ spectroscopic techniques have been used to examine the state of these transition metal macrocycle layers on carbon, graphite and metal substrates under various electrochemical conditions. These techniques have Included (a) visible reflectance spectroscopy (b) laser Raman spectroscopy, utilizing surface enhanced Raman scattering and resonant Raman and (c) Mossbauer spectroscopy. This paper will focus on principally the cobalt and Iron phthalocyanlnes and porphyrins. 

This study could be extended to the synthesis of iron nanoparticles. Using Fe[N(SiMe3)2]2 as precursor and a mixture of HDA and oleic acid, spherical nanoparticles are initially formed as in the case of cobalt. However, a thermal treatment at 150 °C in the presence of H2 leads to coalescence of the particles into cubic particles of 7 nm side length. Furthermore, these particles self-organize into cubic super-structures (cubes of cubes Fig. ) [79]. The nanoparticles are very air-sensitive but consist of zerovalent iron as evidenced by Mossbauer spectroscopy. The fact that the spherical particles present at the early stage of the reaction coalesce into rods in the case of cobalt and cubes in the case of iron is attributed to the crystal structure of the metal particles hep for cobalt, bcc for iron. 

The nuclear decay of radioactive atoms embedded in a host is known to lead to various chemical and physical after effects such as redox processes, bond rupture, and the formation of metastable states [46], A very successful way of investigating such after effects in solid material exploits the Mossbauer effect and has been termed Mossbauer Emission Spectroscopy (MES) or Mossbauer source experiments [47, 48]. For instance, the electron capture (EC) decay of Co to Fe, denoted Co(EC) Fe, in cobalt- or iron-containing compormds has been widely explored. In such MES experiments, the compormd tmder study is usually labeled with Co and then used as the Mossbauer source versus a single-line absorber material such as K4[Fe(CN)6]. The recorded spectrum yields information on the chemical state of the nucleogenic Fe at ca. 10 s, which is approximately the lifetime of the 14.4 keV metastable nuclear state of Fe after nuclear decay. 

In order to dissipate the recoil energy Mossbauer was the first to use atoms in solid crystal lattices as emitters and also to cool both emitter and absorber. In this way it could be shown that the 7-ray emission from radioactive cobalt metal was absorbed by metallic iron. However, it was also found that if the iron sample were in any other chemical state, the different chemical surroundings of the iron nucleus produce a sufficient effect on the nuclear energy levels for absorption no longer to occur. To enable a search for the precisely required absorption frequency, a scan based on the Doppler effect was developed. It was noted that a velocity of 102 ms-1 produced an enormous Doppler shift and using the same equation (7) it follows that a readily attainable displacement of the source at a velocity of 1 cms-1 produces a shift of 108 Hz. This shift corresponds to about 100 line-widths and provides a reasonable scan width. 

Figure 3.26 Cobalt-57 source of 14.41-keV y radiation used in Mossbauer experiments. Isomer shift and quadrupole splitting characteristics are shown at right. (Adapted from Figure 2.26 of reference 3 and Figure 1 of reference 24.)...

The most direct information on the state of cobalt has come from Mossbauer spectroscopy, applied in the emission mode. As explained in Chapter 5, such experiments are done with catalysts that contain the radioactive isotope 57Co as the source and a moving single-line absorber. Great advantages of this method are that the Co-Mo catalyst can be investigated under in situ conditions and the spectrum of cobalt can be correlated to the activity of the catalyst. One needs to be careful, however, because the Mossbauer spectrum one obtains is strictly speaking not that of cobalt, but that of its decay product, iron. The safest way to go is therefore to compare the spectra of the Co-Mo catalysts with those of model compounds for which the state of cobalt is known. This was the approach taken... 

Figure 9.19 In situ Mossbauer emission spectra of 57Co in (left) a series of sulfided Co-Mo/A1203 catalysts and (right) MoS2 particles doped with different amounts of cobalt, corresponding to Co/Mo ratios of a) about 3 parts per million, b) 0.05 and c) 0.25. The Co-Mo-S phase, active in the HDS reaction, has a spectrum unlike that of any bulk cobalt sulfide and is most clearly observed in the spectra of Co-Mo/Al203 catalysts of low Co content, and in the MoS2 particles doped with ppms of cobalt (from Wivel et al. [70] and Topspe et al. [71]).

Figure 9.20 Correlation between the activity of a series of Co-Mo/AI203 catalysts for the HDS reaction, expressed in the reaction rate constant /cT, and the cobalt phases observed in Mossbauer spectra (left) as well as the NO adsorption sites probed with infrared spectra of adsorbed NO (right) (left figure from Wivel et al. [70], right figure adapted from [49] and [74]).

What is the structure of this Co-Mo-S phase A model system, prepared by impregnating a MoS2 crystal with a dilute solution of cobalt ions, such that the model contains ppms of cobalt only, appears to have the same Mossbauer spectrum as the Co-Mo-S phase. It has the same isomer shift (characteristic of the oxidation state), recoilfree fraction (characteristic of lattice vibrations) and almost the same quadrupole splitting (characteristic of symmetry) at all temperatures between 4 and 600 K [71]. Thus, the cobalt species in the ppm Co/MoS2 system provides a convenient model for the active site in a Co-Mo hydrodesulfurization catalyst. 

J. van de Loosdrecht, P. J. van Berge, M. W. J. Craje and A. M. van der Kraan, The application of Mossbauer emission spectroscopy to industrial cobalt based Fischer-Tropsch catalysts, Hyperfine Interact., 2002, 139/140, 3-18. 

X-Ray Absorption Fine Structure, Mossbauer, and Reactivity Studies of Unsupported Cobalt-Molybdenum Hydrotreating Catalysts... 

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.). 

In Situ Mossbauer Measurement on Hematite/Divalent Co-57. The adsorption behavior of cobaltous ions on hematite surfaces was essentially the same as that on silica reported by James and Healy (12). Appreciable adsorption begins at about pH 4 followed by an abrupt increase in adsorption between pH 6 and 8. Beyond pH 9, adsorption is practically complete. Emission Mossbauer spectra of Fe-57 arising from the divalent Co-57 ions at the interface between hematite particles and the 0.1 mol/dm3 NaCl solutions of different pH at room temperature are shown in Figure 3 The emission spectra show a marked dependence on the pH of the aqueous phase. No emission lines ascribable to paramagnetic iron species are recognized in... 

The present method is still in its early stage of application. Both ex situ and in situ type measurements are applicable to a variety of mineral/aqueous solution interfaces. For example, the mechanism of selective adsorption of cobaltous ions on manganese minerals can be studied by this method. In addition to the two Mossbauer source nuclides described in the present article, there are a number of other nuclides which can be studied. We have recently started a series of experiments using Gd-151 which is a source nuclide of Eu-151 Mossbauer spectroscopy. Development of theory on surface magnetism, especially one including relaxation is desirable. Such a theory would facilitate the interpretation of the experimental results. 

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