G. N. Baeva

Aqueous-phase reforming of xylitol over Pt/C and Pt/TiC-CDC catalysts: catalyst characterization and catalytic performance

The aqueous phase reforming (APR) of xylitol was studied over five Pt/C catalysts. The correlation between physico-chemical properties of the catalysts and catalytic performance was established. The Pt/C catalysts have different textural properties as well as different mean Pt cluster sizes and surface acidity. The average Pt cluster size was investigated by means of CO chemisorption as well as by TEM. The reaction was found to be structure sensitive and TOF linearly increases with increasing average Pt cluster size in the studied domain. The catalysts which possess higher surface acidity favoured higher rates of hydrocarbon production. On the contrary the Pt/C materials with lower acidities generated hydrogen with high selectivity and TOF.

Specific features of the catalytic behavior of supported palladium nanoparticles in heterogeneous catalytic reactions

Specific features of the catalytic behavior of supported palladium nanoparticles were analyzed in terms of both the size of the particles and their interaction with the support. The influence of these factors on the activity and selectivity of palladium nanoparticles in carbon-carbon bond hydrogenolysis, hydrogenation of aromatic compounds, olefins, and acetylenes, hydrodechlorination, as well as complete oxidation of organic compounds was discussed. It was shown that the optimal nanoparticle size depends on the type of the reaction and also such factors as the nature of interaction between the nanoparticles and support, absorptivity of the substrates and catalytic reaction products, and electronic and crystal structure of the nanoparticles.

New high-selectivity hydrogenation catalysts prepared from bimetallic acetate complexes

The catalytic properties of new Pd-Zn/Al2O3 catalysts in selective acetylene hydrogenation in an acetylene-ethylene mixture at 30–120°C and atmospheric pressure are reported. The catalysts prepared from the bimetallic complex Pd-Zn(OOCMe)4(OH2) are much more selective than the catalysts prepared by simultaneously supporting the homonuclear complexes Pd3(OOCMe)6 and Zn(OOCMe)2 · 2H2O. It is demonstrated by diffuse reflectance IR spectroscopy of adsorbed CO that the heat treatment of the supported bimetallic complex at 250°C in flowing H2 yields a Pd-Zn alloy on the surface. It is this alloy that ensures the high selectivity of the Pd-Zn/Al2O3 catalysts.

Pd–Cu catalysts from acetate complexes in liquid-phase diphenylacetylene hydrogenation

Properties of Pd–Cu/Al2O3 catalysts prepared using PdCu(CH3CO2)4 acetate heteronuclear complexes as precursors in the liquid-phase diphenylacetylene (DPA) hydrogenation have been studied. It has been established that the reaction over the Pd–Cu/Al2O3 catalyst proceeds more selectively than over the commercial Lindlar catalyst; in addition, high activity is achieved at a substantially lower palladium content. The maximum selectivity of DPA hydrogenation is observed with the catalyst reduced in a hydrogen atmosphere without any intermediate calcination that can result in the destruction of the bimetallic acetate complex. FTIR spectroscopy data for adsorbed CO show that the high selectivity of hydrogenation is due to the formation of homogeneous Pd–Cu particles and to the absence of monometallic palladium particles. This can be explained by the retention of the initial complex structure at all of the catalyst preparation stages until the formation of bimetallic particles during hydrogenation.

Effect of electron irradiation on the catalytic properties of supported Pd catalysts

The effect of electron irradiation on the properties of the systems 1% Pd/C, 1% Pd/Al2O3, and 1% Pd/TiO2 is studied in gas-phase and liquid-phase toluene hydrogenation. An increase in the irradiation dose to 120–900 Mrad increases the catalytic activity by a factor of 2–8 relative to that of the original system. XPS data for the Pd/C catalyst suggest that, after irradiation with high-energy electrons, the metal particles are stabilized on the surface of the carbon support, their degree of dispersion is increased, and their sintering is suppressed. These inferences are consistent with the observed changes in catalytic properties.

Dependence of the catalytic activity of Ag/Al2O3 on the silver concentration in the selective reduction of NOx with n-hexane in the presence of H2

The activity of 0.25–5% Ag/Al2O3 catalysts in the selective catalytic reduction of nitrogen oxides with n-hexane under the conditions of promotion with a small amount of H2 was studied. It was found that, upon the introduction of ∼1000 ppm of H2 into the reaction mixture, the Ag/Al2O3 samples containing 1–2% Ag exhibited optimum activity and selectivity. It was established that, in the presence of 1000 ppm of H2, the rate of the selective catalytic reduction of NOx was higher by a factor of 10–13, and the onset temperature of the reaction was lower by approximately 100°C. It was found by X-ray photoelectron spectroscopy, temperature-programmed reduction, and UV spectroscopy that the high activity of 1–2% Ag/Al2O3 catalysts was due to the presence of small Agnδ+ and Agm0 clusters on their surface. A decrease in the concentration of Ag below the optimum value resulted in the predominance of an inactive ionic form on the catalyst surfaces. As the concentration of Ag was increased (>2%), large particles of Ag2O and Ag0, which facilitate the oxidation of n-C6H14, were formed to lead to a decrease in selectivity and in the degree of reduction of nitrogen oxides.

Supported catalysts based on Pd–In nanoparticles for the liquid-phase hydrogenation of terminal and internal alkynes: 1. formation and structure

The formation of Pd–In catalysts synthesized from the heteronuclear acetate complex PdIn(CH3COO)5 was studied by temperature-programmed reduction, electron microscopy, IR spectroscopy of adsorbed CO and hydrogen temperature-programmed desorption (H2-TPD). IR spectroscopy of adsorbed CO and H2-TPD confirmed the formation of bimetallic Pd–In nanoparticles. It was found that the Pd–In nanoparticle surface contains predominantly Pd atoms separated from one another by indium atoms, which is evidenced by the disappearance of the CO band shift resulting from the lateral dipole–dipole interaction between adsorbed CO molecules and by a significant decrease in the band intensity of CO adsorbed in bridged form. Almost complete inhibition of palladium hydride (PdHx) provides additional evidence of the formation of Pd–In bimetallic particles.

Supported catalysts based on Pd–In nanoparticles for the liquid- phase hydrogenation of terminal and internal alkynes: 2. catalytic properties

Pd–In/Al2O3 and Pd–In/MgAl2O4 catalysts prepared from dinuclear Pd–In acetate complexes were studied in the hydrogenation of alkyne compounds with different structures. The Pd–In catalysts demonstrate high selectivity in the hydrogenation of internal alkynes comparable with that of the Lindlar catalyst. Similar activity/selectivity characteristics are reached at a significantly lower Pd content. For terminal alkynes, the favorable effect of Indium introduction is considerably less pronounced. An analysis of the In effect on the selectivity and the ratio between the rates of the first and second hydrogenation steps suggests that the reaction selectivity is determined to a large extent by a thermodynamic factor (adsorption–desorption equilibrium between the reactants and the reaction products).

Formation of Pd–Ag nanoparticles in supported catalysts based on the heterobimetallic complex PdAg2(OAc)4(HOAc)4

The formation of Pd–Ag nanoparticles deposited from the heterobimetallic acetate complex PdAg2(OAc)4(HOAc)4 on α-Al2O3, γ-Al2O3, and MgAl2O4 has been investigated by high-resolution trans-mission electron microscopy, temperature-programmed reduction, and IR spectroscopy of adsorbed CO. The reduction of PdAg2(OAc)4(HOAc)4 supported on γ-Al2O3 and MgAl2O4 takes place in two steps (at 15–245 and 290–550°C) and yields Pd–Ag particles whose average size is 6–7 nm. The reduction of the Pd–Ag catalyst supported on α-Al2O3 occurs in a much narrower temperature range (15–200°C) and yields larger nanoparticles (~10–20 nm). The formation of Pd–Ag alloy nanoparticles in all of the samples is demonstrated by IR spectroscopy of adsorbed CO, which indicates a marked weakening of the absorption band of the bridged form of adsorbed carbon monoxide and a >30-cm–1 bathochromic shift of the linear adsorbed CO band. IR spectroscopic data for PdAg2/α-Al2O3 suggest that Pd in this sample occurs as isolated atoms on the surface of bimetallic nanoparticles, as is indicated by the almost complete absence of bridged adsorbed CO bands and by a significant weakening of the Pd–CO bond relative to the same bond in the bimetallic samples based on γ-Al2O3 and MgAl2O4 and in the monometallic reference sample Pd/γ-Al2O3.

Formation of supported intermetallic nanoparticles in the Pd–Zn/α-Al2O3 catalyst

The structure of the Pd–Zn/α-Al2O3 catalyst, which was prepared by a joint impregnation method, was studied. According to XRD analysis data, supported intermetallic Pd–Zn particles were formed in a temperature range of 200–600°C. At 600°C, the crystal lattice of substitutional solid solution based on Pd (FCC) was finally rearranged into the tetragonal lattice of Pd–Zn. A shift of the Pd3d5/2 line in the XPS spectrum indicated the formation of the Pd–Zn intermetallic compound.