Kinetic studies on the hydrogenation of nitrate in water using Rh/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Rh-Cu/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Liquid-phase reduction NO ₃ ⁻ using monometallic and bimetallic catalysts (5% Rh/Al₂O₃, 5% Rh-0.5% Cu/Al₂O₃, 5% Rh-1.5% Cu/Al₂O₃, 5% Rh-5% Cu/Al₂O₃ and a physical mixture of 5% Rh/Al₂O₃ and 1.5% Cu/Al₂O₃) was studied in a slurry reactor operating at atmospheric pressure. Kinetic measurements were performed for a low concentration of nitrate (0.4 × 10⁻³−3.2 × 10⁻³ mol dm⁻³) and the temperature range 293–313 K. From the experimental data, it was found that the reduction of nitrate is first order with respect to nitrate. On the basis of the rate constants, the apparent activation energy was established using a graphic method. Published in Russian in Kinetika i Kataliz, 2007, Vol. 48, No. 6, pp. 881–886. This article was submitted by the authors in English.     

Temperature-programmed desoprtion of H2 from the surfaces of pd/support and Pd-Ag/support catalysts (support = Al2O3, SiO2)

Thermal desorption of H₂ from the surface of Pd/support and Pd-Ag/support (support = Al₂O₃, SiO₂) catalysts has been investigated. Two wide desorption peaks can be observed for the 5% Pd/support catalyst. The presence of these peaks in the thermogram indicates that several adsorption states exist, which is the result of occurrance of different adsorption centers of specific bond strengths for hydrogen. The addition of silver to the palladium catalysts causes a considerable decrease in the size of the high temperature desorption peak. It is also worth noting that the temperature of the maximum of the desorption rate remains practically constant for all bimetallic catalysts studied. This means that the activation energy of the hydrogen desorption process does not change after the introduction of silver to the palladium catalyst.     

Study of CO and H2 sorption on supported bimetallic Pd?Pb catalysts

With increasing the lead content both CO and hydrogen sorption drop considerably. The influence of lead can be observed starting from a concentration of 0.5%. This may indicate that the surface is enriched in lead atoms.

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CO, H₂. , 0,5%. .

     

Selective Oxidation of Glucose to Gluconic Acid over Bimetallic Pd–Me Catalysts (Me = Bi,Tl, Sn,Co)

Catalytic properties of bimetallic Pd–Bi, Pd–Tl, Pd–Sn, and Pd–Co catalysts supported on C (from plum stones) and SiO₂ were studied in the reaction of glucose oxidation to gluconic acid. Catalysts modified with Bi show the best selectivity and activity. The results obtained from research on 5% Pd–5% Bi/C and 5% Pd–5% Bi/SiO₂ catalytic systems were compared with the results for a commercial catalyst containing 1% Pt–4% Pd–5% Bi supported on active carbon (Degussa). For both Pd–Bi/support catalysts and 1% Pt–4% Pd–5% Bi/C, similar selectivity in the reaction of glucose oxidation was observed. XRD studies proved the presence of intermetallic compounds BiPd and Bi₂Pd, which probably increase the selectivity of PdBi/SiO₂ catalysts.     

Interaction between Pd and Ag on the surface of silica

Palladium, silver and palladium–silver catalysts supported on silica were prepared by coimpregnation of support with solution of AgNO₃ and Pd(NO₃)₂. The catalysts were characterized by X-ray powder diffraction (XRD), temperature programmed reduction (TPR), time of flight ion mass spectrometry (ToF-SIMS), chemisorption of carbon monoxide and were tested in the reaction of selective oxidation of glucose to gluconic acid.

XRD and TPR studies have shown that an interaction between Pd and Ag on the surface of silica after oxidation at 500 °C and reduction at 260 °C leads to the formation of solid solutions.

ToF-SIMS images of the surface of 5% Ag/SiO₂ catalyst after oxidation at 500 °C and reduction at 260 °C show that Ag atoms supported on silica are not distributed homogenously but tend to form regions of enhanced Ag concentration. Positive ions images of the surface of 5% Pd/SiO₂ catalyst also display regions of enhanced concentration of Pd atoms, but they are more homogenously distributed on silica.

ToF-SIMS peak intensity ratio ¹⁰⁸Pd⁺/¹⁰⁷Ag⁺ for bimetallic 5% Pd–5% Ag/SiO₂ catalysts has a lower value than that obtained for physical mixture 5% Pd/SiO₂–5% Ag/SiO₂ which indicates that the surface of bimetallic catalyst is enriched with silver atoms.     

Investigation of Pd?Pb/Al2O3 catalysts by temperature-programmed reduction

Temperature-programmed reduction has been used to characterize, a series of Pd–Pb/Al₂O₃ catalysts. Oxidation and thermal decomposition of bimetallic Pb–Pb/Al₂O₃ catalysts in a stream of argon leads to segregation of individual oxides. Reduction of PdO–PbO/Al₂O₃ occurs at the same temperature as that found for PdO/Al₂O₃ and PbO/Al₂O₃. TPR measurement after isothermal reduction at 823 K and reoxidation point to bimetallic interaction between palladium and lead atoms only for small percentages of palladium.

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- () Pd–Pb/Al₂O₃. PdO–Pb/Al₂O₃ . PdO–PbO/Al₂O₃ PdO/Al₂O₃ PbO/Al₂O₃. - 823 — .

     

Thermal desorption of hydrogen and carbon monoxide from Pd?Pb/Al2O3 catalysts

Thermal desorption of CO and H₂ from the surface of Pd/Al₂O₃ and Pd–Pb/Al₂O₃ catalysts has been investigated. No significant effects of adding lead to palladium catalysts on the activation energy of desorption process have been observed.

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CO H₂ Pd/Al₂O₃ Pd–Pb/Al₂O₃. - .

     

Thallium as an Additive Modifying the Selectivity of Pd/SiO2 Catalysts

Catalytic properties of palladium and bimetallic palladium–thallium catalysts supported on SiO₂ in the reaction of glucose oxidation to gluconic acid were studied. Catalysts modified with thallium showed better selectivity and activity than palladium catalysts. XRD studies proved the presence of intermetallic interactions, which probably increase the selectivity of Pd–Tl/SiO₂ catalysts. Particular attention was paid to the losses of thallium and palladium from the catalysts during the catalytic reaction.     

Hydrogenation of nitrate in water over bimetallic Pd-Ag/Al2O3 catalysts

Hydrogenation of nitrate (NO₃ ⁻) in water was studied with 0.8 ×10⁻³–3.2 ×10⁻³ mol/dm³ of reactant in the temperature range of 293–313 K over palladium promoted Ag catalysts. Pd-Ag catalysts with a low ratio of Ag/Pd were characterized by high efficiency in the reduction of nitrates. The degradation of nitrates followed approximately first order decay and the estimated apparent activation energy was about 4 kJ/mol.