Cobalt EXAFS

X-ray diffraction patterns and the cobalt EXAFS spectra of C03O4 and the calcined catalysts were indistinguishable within experimental error, consistently showing that C03O4 is the predominant cobalt species after calcination. 

The introduction of redox activity through a Co11 center in place of redox-inactive Zn11 can be revealing. Carboxypeptidase B (another Zn enzyme) and its Co-substituted derivative were oxidized by the active-site-selective m-chloroperbenzoic acid.1209 In the Co-substituted oxidized (Co111) enzyme there was a decrease in both the peptidase and the esterase activities, whereas in the zinc enzyme only the peptidase activity decreased. Oxidation of the native enzyme resulted in modification of a methionine residue instead. These studies indicate that the two metal ions impose different structural and functional properties on the active site, leading to differing reactivities of specific amino acid residues. Replacement of zinc(II) in the methyltransferase enzyme MT2-A by cobalt(II) yields an enzyme with enhanced activity, where spectroscopy also indicates coordination by two thiolates and two histidines, supported by EXAFS analysis of the zinc coordination sphere.1210... 

Jacobs G., Ji Y., Davis B.H., Cronauer D., Kropf J., and Marshall C.L. 2007. Fischer-Tropsch synthesis Temperature programmed EXAFS/XANES investigation of the influence of support type, cobalt loading and noble metal promoter addition to the reduction behaviour of cobalt oxide particles. Appl. Catal. A Gen. 333 179-91. 

The results confirm that the novel metal nitrate conversion method using nitric oxide in place of air advocated by Sietsma et al. in patent applications WO 2008029177 and WO 2007071899 leads to, after activation in H2, catalysts with smaller cobalt crystallites, as measured by EXAFS and hydrogen chemisorption/ pulse reoxidation. In spite of the lower extent of cobalt reduction for H2-activated nitric oxide calcined catalysts, which was recorded by TPR, XANES, EXAFS,... 

Ronning, M., Nicholson, D.G., and Holmen, A. 2001. In situ EXAFS study of the bimetallic interaction in a rhenium-promoted alumina-supported cobalt Fischer-Tropsch catalyst. Catal. Lett. 72 141 -6. 

In order to draw a crystallographic picture of the Co-Mo-S phase, we need precise data on the location of the cobalt atom with respect to the molybdenum and the sulfur atoms. For this, EXAFS is the indicated technique. 

Several groups [64-67,76] have reported EXAFS studies on sulfided cobalt-molybdenum catalysts. Figure 9.22 shows the Fourier transforms of M0S2 and of sulfided molybdenum and cobalt-molybdenum catalysts supported on carbon,... 

The EXAFS signal from the Co K edge gives information on the surroundings of cobalt. As an active sulfided Co-Mo/AI2O3 catalyst contains at least two cobalt species, namely ions inside the A1203 lattice and in the Co-Mo-S phase, it is better to investigate the Co-Mo-S phase in carbon-supported catalysts. The latter can be... 

The Co/Mo = 0.125 catalyst has all the cobalt atoms present as Co-Mo-S and, therefore, the EXAFS studies of this catalyst can give information about the molybdenum atoms in the Co-Mo-S structure. The Fourier transform (Figure 2c) of the Mo EXAFS of the above catalyst shows the presence of two distinct backscatterer peaks. A fit of the Fourier filtered EXAFS data using the phase and amplitude functions obtained for well-crystallized MoS2 shows (Table II) that the Mo-S and Mo-Mo bond lengths in the catalyst are identical (within 0.01 A) to those present in MoS2 (R =... 

The EXAFS data recorded after exposure to air of the unsupported Co-Mo catalysts with different cobalt content allow one to examine the effect of cobalt. In spite of a great uncertainty in the coordination numbers, the promoted catalysts seem to have a somewhat smaller domain size than the unpromoted catalyst as indicated both by the smaller second shell coordination numbers and by the larger effect of air exposure (i.e., reduced sulfur coordination number in first shell). This influence of cobalt on the domain size may be related to the possibility that cobalt atoms located at edges of M0S2 stabilize the domains towards growth in the basal plane direction. Recent results on C0-M0/AI2O3 catalysts indicate that Co may also have a similar stabilizing effect in supported catalysts (36). 

EXAFS data at the Co and Al K edges for Co Al - Cl LDHs were consistent with an ordered array of cations for n = 2,3 and 4. In each case the Al has a second coordination shell of 6 Co ions and the Co has a second shell of 6/n Al and (6-6/ ) Co next nearest neighbors [46]. The peaks arising from the focusing effect are still observed in the Co K edge EXAFS of the material showing that the cobalt cations in the layers remain ahgned. 

Co2(CO)g has been used to obtain encapsulated cobalt clusters in Y-faujasite, which have been used as model catalysts for methane homologation [152]. The gas phase adsorption of Co2(CO)8 under N2 rendered predominately encaged Co4(CO)i2 species whereas Co,s(CO)iis was obtained when the impregnation of Co2(CO)8 was carried out under a CO/H2 atmosphere [152, 155], Samples were oxidized at 80°C, subsequently reduced at 400 °C and then structurally characterized by EXAFS. Clusters of two and three cobalt atoms were formed from encaged Co4(CO)i2 and COis(CO)iis, respectively. Higher methane conversion and selectivity to C2+ products in the CH4 homologation reaction have been obtained for the two atoms-size cluster sample the results were discussed using a DFT model [152]. 

Fig. 6a-c. One monolayer of cobalt on copper (111), grazing incidence, T = 77 K and T = 300 K relevant steps of the EXAFS analysis, a Experimental absorption spectra b fourier transform of the EXAFS oscillations c inverse Fourier transform of the first neighbour peak as a function of photoelectron kinetic energy E... 

EXAFS has provided detailed information about the local environment of the active Co and Ni sites and the Mo atoms to which they are attached in terms of the types of atoms within two atomic shells away from the atom being characterized. Cobalt and nickel were shown to be definitely bonded to the surfaces of small MoS2 crystallites. Representative structures for the environments of Mo and Co are illustrated in the following diagram. In such structures, Mo has a coordination number (CN) of 6, with six nearneighbor sulfur atoms, three nearby Mo atoms, and one nearby Co or Ni atom. Co-S configurations were either CN = 5 (square pyramidal) or CN = 6 (octahedral), with either one nearby Mo atom (low HDS activity) or two nearby Mo atoms (high HDS activity) (62). 

Figure 1 shows Fourier transforms of EXAFS spectra of a few samples prepared. The radial distribution functions of these samples are different from that of nickel oxide or cobalt oxide [7]. All the Fourier transforms showed two peaks at similar distances (phase uncorrected) the peak between 1 and 2 A is ascribed to the M-0 bond (M divalent cation) and the peak between 2 and 3 A is ascribed to the M-O-M and M-O-Si bonds. The similar radial distribution functions in Figure 1 indicate that the local structures of X-ray absorbing atoms (Ni, Co, and Zn) are similar. No other bonds derived from metal oxides (nickel, cobalt and zinc oxides) were observed in the EXAFS Fourier transforms of the samples calcined at 873 K, which suggests that the divalent cations are incorporated in the octahedral lattice. 

Table 1 shows the properties of smectite-type materials prepared. Smectite materials prepared at lower pH had fewer sodium ions, higher surface areas, and larger pore volumes for a series of samples containing the same divalent cation species (nickel and cobalt) in the octahedral sheet. The adsorption of methylene blue on all the synthetic smectites shows that the smectite fragments are negatively charged. The Si M ratios of synthetic smectites were about 8 6, indicating that most of divalent cations exist in octahedral layers and small amount of divalent cations would exist as hydroxide or oxide cluster in smectite materials. However, the amounts of the hydroxide or oxide cluster were small, because only smectite structures were observed in XRD patterns and EXAFS Fourier transforms of synthetic smectites calcined at 873 K. 

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