Co(Ni)/MoS2 nanostructured catalysts for the hydrodesulphurization of dibenzothiophene.

In this study Co(Ni)/MoS2 unsupported nanocatalysts (nanorods and nanoribbons) were synthesized with Co(Ni)/(Co(Ni) + Mo) = 0.3, 0.5 molar ratios for Co and Ni respectively. First the alpha-MoO3 nanostructures were impregnated with an aqueous solution of Co(Ni)Cl2 x 6H2O or Co(Ni)(NO3)2 x 6H2O, then were treated for 2 h at 473 K, and finally the precursors were activated under a H2S/H2 mixture (15% v/v H2S) by ramping the temperature from room temperature to 773 K and keeping it at that value for 2 h. The resulting materials were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, transmission electron microscopy, X-ray diffraction, specific surface area and X-ray photoelectron spectroscopy, and tested as catalysts for the hydrodesulfurization (HDS) of dibenzothiophene (DBT). It was found that these materials presented specific surface areas below 25 m2/g. The catalytic test showed that only when Co is added a promoter effect is observed compared with MoS2 unpromoted catalysts. Among the materials prepared, the Co/MoS2 catalyst made from cobalt chloride presented the highest catalytic activity (6.95 mol s(-1) g(-1)catalyst) for the HDS of DBT. The selectivity for the latter indicated a clear preference for the direct desulphurization over the hydrogenating pathway.

Dynamic Monte Carlo simulation of the NO + CO reaction on Rh(111).

The kinetics of the catalytic reduction of NO by CO on Rh(111) surfaces was investigated by using dynamic Monte Carlo simulations. Our model takes into account recent experimental findings and introduces relevant modifications to the classical reaction scheme, including an alternative pathway to produce N2 through an (N-NO)* intermediate, the formation of atomic nitrogen islands in the adsorbed phase, and the influence of coadsorbed species on the dissociation of NO. All elementary steps are expressed as activated processes with temperature-dependent rates and realistic values dictated by experiments. Calculated steady-state phase diagrams are presented for the NO + CO reaction showing the windows for the conditions under which the reaction is viable. The model predicts variations in both production rates and adsorbate coverages with temperature consistent with experimental data. The effect of varying the individual kinetic parameters and the importance of each step in the reaction scheme were probed.

Differential-polarization dual-beam FT-IR spectrometer for surface analysis.

A new system for reflection-absorption Fourier transform infrared spectroscopy is described. It is based on an optical subtraction of the two output beams of a cube-corner interferometer, which are recombined, orthogonally polarized and passed onto a single detector, where only the difference signal of the two components is detected. The dynamic range of the signal is thereby reduced by at least an order of magnitude. Owing to the cube-corner reflectors the dual-beam optics are relatively simple and readily convertible for operation in the conventional single-beam mode. First results with an incompletely optimized system show high photometric accuracy and equal signal-to-noise ratio compared to the single-beam operation. Methods for further improving its performance are proposed.