Cristina Cerdá-Moreno

In this paper, substituted anilines are industrially obtained by direct hydrogenation of nitroaromatic compounds with molecular H₂ using metals as catalysts. Previous theoretical studies proposed that the mechanism of the reaction depends on the nature of the metal used as a catalyst, and that rationally designed bimetallic materials might show improved catalytic performance. Herein, we present IR spectroscopic studies of nitrobenzene interactions with monometallic Ni/SiO₂, Cu/SiO₂ and Pd/SiO_2, and with bimetallic CuNi/SiO₂ and CuPd/SiO₂ catalysts, both in the absence and presence of H₂, combined with density functional theory (DFT) calculations on selected bimetallic NiCu(111) and PdCu(111) models. The results obtained experimentally confirm that the reaction mechanism on non-noble metals such as Ni proceeds through N-O bond dissociation, generating nitrosobenzene intermediates, while, on noble metals, such as Pd, H-attack is necessary to activate the NO bond. Moreover, a bimetallic CuPd/SiO₂ catalyst with a Pd enriched surface is prepared that exhibits an enhanced H₂ dissociation ability and a particular reactivity at the boundary between the two metals.

The urgent need to reduce CO₂ emissions requires the development of efficient catalysts for the conversion of CO₂ into chemicals and fuels. In this study, a series of nickel catalysts supported on ITQ-2 and ZSM-5 zeolites have been prepared, characterized and tested in the hydrogenation reaction of CO₂ towards methane. Specifically, two ITQ-2 and two ZSM 5 zeolites with different aluminum content have been studied. For both types, the higher Si/Al ratio of the material, the more active the catalyst due probably to its higher hydrophobicity. The largest difference was found for the ITQ-2 samples, being the CO₂ conversion for the sample with a greater Si/Al ratio 50 points higher at 350 °C. Comparing both zeolite structures, while similar catalytic results were obtained with the samples with lower Si/Al ratio, a distinctly higher activity was found for the ITQ-2 zeolite without aluminum, pure silica. Therefore, this result suggests that the presence of aluminum is of particular relevance. Among the studied materials, the catalyst supported on the delaminated ITQ-2 zeolite without Al was the most active catalyst. Its higher activity was mainly attributed to the smaller crystallite size of nickel supported on the large external surface area presented by this zeolite.