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• Controllable activity and selectivity of Pd/C hydrogenation catalysts. • Effect of the carbon support on the structure and catalytic properties of Pd NPs. • Effect of the Pd precursor on the structure and catalytic properties of Pd NPs. • Addition of a second metal and the synergistic effect in Pd-based bimetallic catalysts. Carbon-supported palladium catalysts are widely used for hydrogenation of various organic compounds in the fine chemical industry. The nanoscale geometry and electronic structure of supported Pd nanoparticles play a crucial role in providing the necessary catalytic properties. To improve catalytic activity and selectivity of Pd nanoparticles, it is possible to fine tune their intrinsic properties (e.g., size and oxidation state) by controlling the chemical transformations at different stages of catalyst preparation. Recent years have seen considerable advancement in developing new catalyst preparation techniques as well as in understanding the mechanism of active site formation. This review summarizes some of the existing approaches to regulating the catalytic properties of carbon-supported palladium by variation of the carbon support, the composition of palladium precursor and its reduction conditions, as well as the addition of a second active metal. The data presented may be useful for researchers developing efficient Pd/C catalysts for hydrogenation of polyfunctional organic compounds. [ABSTRACT FROM AUTHOR]

Abstract: The mechanism of the propylene oxidation by Pd(NOn)Cl2−m(CH3CN)2 complexes (n=2,3; m=0,1,2) in chloroform solutions has been studied by 1H NMR and IR spectroscopy. The main reaction products are acetone and 2-nitropropylene, with their ratio depending on the equilibrium existing in the reaction solutions between palladium complexes containing NOn ligands bonded to a palladium atom via either an oxygen or a nitrogen atom. Reactivities of the oxygen bonded nitrato and nitrito complexes are significantly higher than that of the nitrogen bonded nitro complex. Various new organopalladium intermediates have been observed and monitored in situ. A reversible insertion of the coordinated propylene into the Pd–O or Pd–N bonds results in nitrato-, nitrito- and nitropalladation intermediates, which then decompose via a β-hydrogen elimination. Two isomers of the nitritopalladation intermediate have been detected, i.e., a palladium metallacycle and an open ring complex, with the latter being much more reactive towards the β-hydrogen elimination than the former. The decomposition of the nitrato- and nitritopalladation intermediates results in the organometallic precursor of acetone, i.e., an acetonylpalladium complex, and then in acetone itself. On the other hand, the nitropalladation intermediate originates 2-nitropropylene. In the presence of dioxygen, which re-oxidizes the nitrosyl groups, the acetone formation becomes a catalytic reaction with respect to both palladium and nitrogen. [Copyright &y& Elsevier]

• MgAl-layered hydroxides were synthesized on the surface of γ-Al 2 O 3 using its Al atoms. • Modification of alumina changed the mechanism of [PtCl 6 ]2− anchoring. • Adsorption occurs with localization of 2–4 nm platinum particles in the MgAl-phase. • Catalyst with supported LDH provides a higher stability in propane dehydrogenation. Layered magnesium-aluminum hydroxides of hydrotalcite-like structure were synthesized on the surface of γ-Al 2 O 3. The synthesis was performed via the interaction of aluminum and magnesium hydroxides and carbonate ions in the pores of alumina support. Novelty of the approach was that the synthesis involved the boehmite phase AlO(OH) that formed directly on the surface of γ-Al 2 O 3 under hydrothermal conditions. This approach provides fixation of the forming layered phase on the surface of initial support and retains textural parameters of the support. The formation of a layered structure on the γ-Al 2 O 3 surface was confirmed by XRD analysis and electron microscopy studies. Investigation of the H 2 [PtCl 6 ] anchoring on γ-Al 2 O 3 with supported magnesium-aluminum hydroxide by UV–vis DRS, 195Pt NMR and HRTEM showed that platinum was adsorbed on the surface as chloride forms of the complexes with a low degree of hydrolysis even at a low metal content. Catalytic properties of the synthesized supported platinum catalysts were examined in a model reaction of propane dehydrogenation. In comparison with the alumina-platinum catalyst, the modified sample showed a better stability at a somewhat higher yield of propylene because the formation of heavy products was suppressed. [ABSTRACT FROM AUTHOR]

Carbon nanofibers (CNFs) have been rapidly synthesized on the surface of low-cost commercial chlorinated polymers (chlorinated polyvinyl chloride, polyvinyl chloride), which contains iron compounds, under the action of a high power ion beam at room temperature. Organic (Fe(C 5 H 5 ) 2 ) and inorganic (FeCl 3 ⋅6H 2 O и Fe(NO 3 ) 3 ·9H 2 O) iron compounds were used as catalytic additions. SEM, TEM and Raman spectroscopy were used to investigate the morphologies and structure of irradiated polymers. CNFs had a most probable diameter in the range 50–90 nm and a maximum length of up to 10 μm. The maximum CNFs growth rate was estimated as 160 μm/μs. A possible growth mechanism for CNFs is discussed. [ABSTRACT FROM AUTHOR]

The palladium catalysts prepared using carbon nanoglobules (CNGs) as the support and containing no more than 2 wt% Pd were shown to be highly effective for the liquid-phase hydrogenation of ethyl 4-nitrobenzoate under mild conditions. Regardless of the kind of CNGs and the catalyst preparation method, the most of the Pd/CNGs catalysts allow achieving a complete conversion of substrate giving benzocaine in a 100% yield. The Pd/CNGs catalyst is easily recycled many times without loss of its catalytic performance. The results obtained may be useful for the development of effective Pd/C catalysts for chemoselective hydrogenation of various nitroarenes. [ABSTRACT FROM AUTHOR]

The effect of the nature of alkaline agent and pH value of hydrolysis of Pd(II) chloride complex into palladium polynuclear hydroxo complexes, as precursor of active component in Pd/C catalyst, on the dispersion of palladium particles supported on carbon material Sibunit was revealed. It was shown that an increase in the particle size of supported palladium enhances the specific catalytic activity in hydrogenation of 2,4,6-trinitrobenzoic acid and changes the direction of the transformation (increases the fraction of non-aromatic intermediate, cyclohexane-1,3,5-trione trioxime, in the products). The results obtained are essential for optimizing the particle size of supported palladium in selective hydrogenation of polyfunctional organic compounds. [ABSTRACT FROM AUTHOR]

Bimetallic Pd-Ru/C catalysts prepared with different carbon supports were shown to be much more active in the liquid-phase hydrogenation of benzaldehyde in comparison with their monometallic analogs. In the case of systems based on nanoglobular carbon, the synergistic effect manifested itself as an increased selectivity for benzyl alcohol (86–90%) at a complete conversion of benzaldehyde, whereas the catalysts containing carbon nanotubes were highly active in hydrogenolysis of the C O bonds, which caused an increased yield of toluene (up to 56%). The synergistic effect between palladium and ruthenium in the reaction under study can be related to the changes in the electronic and dispersion state of the supported metals upon interaction with each other and formation of Pd-Ru alloy. In terms of the electronic factor, the enhanced catalytic performance of bimetallic systems can be a result of facilitation of electrophilic activation of the C O bond in benzaldehyde owing to an increased fraction of the electron-deficient palladium species. The nature of carbon support was shown to affect the electronic state of supported metals and thus catalytic properties of bimetallic Pd-Ru/C systems. [ABSTRACT FROM AUTHOR]

Results of the catalytic hydrogenation of 2,4,6-trinitrobenzoic acid (TNBA) in the presence of 1% Pd/C catalyst with analysis of the reaction products at the steps corresponding to the consumption of 1, 3, 5, 6, 8 and 9 mols of hydrogen per mol of TNBA are presented. Numerous reaction intermediates were identified using the 1 H and 13 C NMR spectroscopy; the reaction mixture composition was assessed quantitatively at different steps of the hydrogenation. The data obtained were used to propose a scheme of TNBA transformations over the Pd/C catalyst in the aqueous-phase reaction conditions. The data on the component composition at different steps of TNBA hydrogenation are important to understand the process chemistry, to explore the possibility of selective formation of different types of intermediate nitroamino compounds, and to synthesize high-performance catalysts for the hydrogenation of aromatic polynitro compounds. [ABSTRACT FROM AUTHOR]

The study considered the formation and catalytic properties of the active sites in Pd/C and Ru/C catalysts supported on carbon nanotubes (CNT) and carbon black (CB). The nature of carbon support was shown to affect the dispersion of supported metal and its catalytic properties in the aqueous-phase hydrogenation of furfural. The 1.5% Pd/CB catalyst demonstrated a high selectivity (99%) for furfuryl alcohol during hydrogenation of furfural at a temperature of 50 °C and hydrogen pressure of 0.5 MPa. The 1.5% Pd/CNT catalyst was not active under mild conditions of the reaction (50 °C, 0.5 MPa), but had a greater tendency to reduce the furan ring under severe conditions (90 °C, 0.5 or 2.0 MPa) as demonstrated by an increased yield of tetrahydrofurfuryl alcohol. The ruthenium samples showed a low activity in aqueous-phase hydrogenation of furfural irrespective of the support nature and reaction conditions, possibly due to irreversible adsorption of water on the active sites. [ABSTRACT FROM AUTHOR]

Highlights: [•] Increase the fraction of bridging OH groups and concentration of Lewis acid sites. [•] Preferential formation of outer-sphere complexes. [•] Changes in the dispersion and electronic state of supported Pt. [•] Effect of hydrothermal treatment of the support on catalytic properties of Pt/Al2O3. [ABSTRACT FROM AUTHOR]

Abstract: A method for in situ reduction of the sulfur content in catalytic cracking gasoline is reported. A comparison of thermal and catalytic transformations of sulfide and thiophene sulfur is presented. Main transformations of various organosulfur compounds are demonstrated. The effect of [H]-donor activity of hydrocarbons on conversion of thiophene sulfur into hydrogen sulfide is revealed. The impact of acid–base properties of the additives to the cracking catalysts on sulfur content reduction in the liquid products is examined in detail (TPD-NH3, 27Al NMR, CO2 adsorption). The choice of optimal qualitative composition of a modifying additive for reducing the sulfur content in catalytic cracking gasoline is substantiated. [Copyright &y& Elsevier]

Abstract: The state of palladium in Pd/SO4 2−–ZrO2 (Pd/SZ) isomerization catalyst was investigated by the temperature-programmed reduction (TPR), chemisorption technique, infrared spectroscopy of adsorbed carbon monoxide (FTIRS), X-ray photoelectron spectroscopy (XPS), diffuse-reflectance UV–vis spectroscopy (UV–vis DRS), and benzene hydrogenation as a test reaction. It has been stated that reduction temperature has a great impact on the metal function of Pd-promoted sulfated zirconia catalyst. Metal centers are formed at about 30–70°C and characterized by high palladium dispersion and activity in benzene hydrogenation. At temperatures above 200°C, intensive sulfate decomposition occurs and products of sulfate reduction poison the metal function of the catalyst. According to XPS and FTIRS study, palladium particles in the poisoned samples are only partly oxidized, but the main part is presented by metallic phase without large amount of PdS. Reduction of Pd-containing catalyst at 150°C (instead of 250°C) leads to higher conversion and 2,2-dimethylbutane yield in acid-catalyzed reaction of n-hexane isomerization. Higher isomerization activity in this case is provided by prevention of active sulfate species decomposition due to the capability of palladium metallic particles formation at low reduction temperatures. [ABSTRACT FROM AUTHOR]

Ni(Mg)Al-layered double hydroxides (LDH) were synthesized by coprecipitation. Structural properties of LDH and mixed oxides Ni(Mg)AlO x , obtained by LDH calcination, were studied by XRD and SEM. Textural properties of Ni(Mg)AlO x were studied by the nitrogen adsorption-desorption method. It was found that the formation of the single-phase LDH was occurred for any nickel content in the samples. The mixed oxides have a high specific surface area, the value of which decreases with increasing nickel content in the samples. Ni(Mg)AlO x are characterized by high activity in furfural hydrogenation. Selectivity of the formation of different reaction products depends on the nickel content in the catalysts. The full furfural conversion with the furfuryl alcohol selectivity no more than 65% was observed for the catalyst with a low nickel content. At the same time an increase in selectivity for furfuryl alcohol up to 84% occurs for the NiAl-catalyst with a furfural conversion not exceeding 43%. [Display omitted] • Synthesis of single-phase Ni(Mg)Al-layered hydroxides by coprecipitation. • Structural and textural properties of the Ni(Mg)Al-layered hydroxides and their calcined forms. • High activity of the Ni(Mg)AlO x catalysts in the reaction of aqua-phase furfural hydrogenation. • Selectivity of products formation can vary by changing the nickel amount in the Ni(Mg)AlO x catalysts. [ABSTRACT FROM AUTHOR]