ABSTRACT
The direct redox reaction (galvanic displacement) between Pd(2+) and substrate Si was used to deposit Pd on Si, and the Pd-Si catalysts enabled a chemoselective hydrogenation of para-chloronitrobenzene with the selectivity for para-chloroaniline higher than 99.9% at complete conversion of para-chloronitrobenzene.
ABSTRACT
Adding a small amount of fully dispersed Pt entities onto the Au surface in Au/SiO(2) catalyst is found to be an efficient approach to improve the catalytic activity of Au (up to 70-fold) for the hydrogenation of α,ß-unsaturated carbonyl compounds, without alternating its selectivity towards C=O or C=C bond hydrogenation.
ABSTRACT
The effect of Au(3+) percentage in Au/TiO(2) on its storage stability at room temperature was studied by varying the drying temperature and storage duration of a deposition-precipitation prepared Au/TiO(2) sample. Carefully-designed room temperature storage in a desiccator, in the dark to exclude any interference of light irradiation, was referenced to the freezing storage (255 K) in a refrigerator. The samples were characterized by well-calibrated H(2)-TPR, TEM and TG measurements. Reduction of Au(3+) ions and agglomeration of metallic Au particles were shown to be the main reasons for the deterioration of Au/TiO(2) during desiccator-storage. Correlating the percentage of Au(3+) ions, determined by H(2)-TPR, with the storage stability of Au/TiO(2) for CO oxidation at 273 K revealed that Au/TiO(2) samples with higher Au(3+) percentages (>90%) were much more stable during the desiccator-storage than those with higher percentages of metallic Au. Residual water in fresh Au/TiO(2) before storage showed a promotional effect on gold reduction and agglomeration during storage. By maximizing the percentage of Au(3+) ions and minimizing the residual water in the fresh sample, the deterioration of the Au/TiO(2) catalyst was successfully avoided during desiccator-storage of up to 150 days in dark. A possible mechanism of Au/TiO(2) deterioration during the desiccator-storage was also discussed.
ABSTRACT
The evolution of nickel speciation during the successive preparation steps of Ni-SiO(2) catalysts is studied by UV-Vis-NIR, FT-IR, DTG, TPR and TEM. The study focuses on the effect of the number of chelating ligands in the precursor complexes [Ni(en)(x)(H(2)O)((6-2x))](2+) (en = ethylenediamine, x = 1, 2, 3) on the adsorption on silica, and on nickel speciation after thermal treatment. When the en:Ni ratio in solution increases from 1 to 3, the most abundant complex is [Ni(en)(H(2)O)(4)](2+) (64% of all Ni complexes), [Ni(en)(2)(H(2)O)(2)](2+) (81%) and [Ni(en)(3)](2+) (61%), respectively. Equilibrium adsorption of [Ni(en)(x)(H(2)O)((6-2x))](2+) on SiO(2) results in the selective grafting of [Ni(en)(H(2)O)(4)](2+) and [Ni(en)(2)(H(2)O)(2)](2+), through the substitution of two labile H(2)O ligands by two surface SiO(-) groups. The surface [Ni(en)(H(2)O)(2)(SiO)(2)] complex formed by the grafting of [Ni(en)(H(2)O)(4)](2+) onto silica tends to transform into NiO and nickel phyllosilicate after calcination, which consequently leads to large and heterogeneously distributed metallic Ni particles upon reduction. In contrast, [Ni(en)(2)(SiO)(2)], resulting from the grafting of [Ni(en)(2)(H(2)O)(2)](2+) onto silica, no longer has aqua ligands able to react with other nickel complexes or silicium-containing species. Calcination transforms these complexes into isolated Ni(2+) ions, which are reduced into small metallic Ni particles with a more homogeneous size distribution, even at higher Ni loading.
