Ultrasound- and microwave-assisted preparation of lead-free palladium catalysts: effects on the kinetics of diphenylacetylene semi-hydrogenation

The effect of environmentally benign enabling technologies such as ultrasound and microwaves on the preparation of the lead-free Pd catalyst has been studied. A one-pot method of the catalyst preparation using ultrasound-assisted dispersion of palladium acetate in the presence of the surfactant/capping agent and boehmite support produced the catalyst containing Pd nanoparticles and reduced the number of pores larger than 4 nm in the boehmite support. This catalyst demonstrated higher activity and selectivity. The comparison of kinetic parameters for diphenylacetylene hydrogenation showed that the catalyst obtained by using the one-pot method was seven times as active as a commercial Lindlar catalyst and selectivity towards Z-stilbene was high. Our work also illustrated that highly selective Pd/boehmite catalysts can be prepared through ultrasound-assisted dispersion and microwave-assisted reduction in water under hydrogen pressure without any surfactant

Use of Desulfovibrio and Escherichia coli Pd-nanocatalysts in reduction of Cr(VI) and hydrogenolytic dehalogenation of polychlorinated biphenyls and used transformer oil

BACKGROUND Desulfovibrio spp. biofabricate metallic nanoparticles (e.g. ‘Bio-Pd’) which catalyse the reduction of Cr(VI) to Cr(III) and dehalogenate polychlorinated biphenyls (PCBs). Desulfovibrio spp. are anaerobic and produce H2S, a potent catalyst poison, whereas Escherichia coli can be pre-grown aerobically to high density, has well defined molecular tools, and also makes catalytically-active ‘Bio-Pd’. The first aim was to compare ‘Bio-Pd’ catalysts made by Desulfovibrio spp. and E. coli using suspended and immobilised catalysts. The second aim was to evaluate the potential for Bio-Pd-mediated dehalogenation of PCBs in used transformer oils, which preclude recovery and re-use.\ud RESULTS Catalysis via Bio-PdD. desulfuricans and Bio-PdE. coli was compared at a mass loading of Pd:biomass of 1:3 via reduction of Cr(VI) in aqueous solution (immobilised catalyst) and hydrogenolytic release of Cl- from PCBs and used transformer oil (catalyst suspensions). In both cases Bio-PdD. desulfuricans outperformed Bio-Pd E. coli by ~3.5-fold, attributable to a ~3.5-fold difference in their Pd-nanoparticle surface areas determined by magnetic measurements (Bio-PdD. desulfuricans) and by chemisorption analysis (Bio-PdE. coli). Small Pd particles were confirmed on D. desulfuricans and fewer, larger ones on E. coli via electron microscopy. Bio-PdD. desulfuricans-mediated chloride release from used transformer oil (5.6 $\pm$ 0.8 $\mu$g mL-1 ) was comparable to that observed using several PCB reference materials. \ud CONCLUSIONS At a loading of 1:3 Pd: biomass Bio-PdD. desulfuricans is 3.5-fold more active than Bio-PdE. coli, attributable to the relative catalyst surface areas reflected in the smaller nanoparticle sizes of the former. This study also shows the potential of Bio-PdD. desulfuricans to remediate used transformer oil

ppm Pd-catalyzed, Cu-free Sonogashira couplings in water using commercially available catalyst precursors.

A new catalyst that derives from commercially available precursors for copper-free, Pd-catalyzed Sonogashira reactions at the sustainable ppm level of precious metal palladium under mild aqueous micellar conditions has been developed. Both the palladium pre-catalyst and ligand are commercially available, bench stable, and highly cost-effective. The catalyst is applicable to both aryl- and heteroaryl-bromides as educts. A wide range of functional groups are tolerated and the aqueous reaction medium can be recycled. An application to a key intermediate associated with an active pharmaceutical ingredient (ponatinib) is discussed

A temperature overshoot on a catalyst pellet

An unexpected temperature overshoot was found for a Pd on alumina catalyst pellet in its course towards a new steady state, after a change in concentration of one of the reactants. The reaction mixture consisted of ethylene, hydrogen and nitrogen as inert. A speculative model is introduced, which can explain these overshoots by a slow adsorption of one of the reactants on the active sites of the catalyst

Biomass-supported catalysts on Desulfovibrio desulfuricans and Rhodobacter sphaeroides

A Rhodobacter sphaeroides-supported dried, ground palladium catalyst (‘‘Rs-Pd(0)’’) was compared with a Desulfovibrio desulfuricans-supported catalyst (‘‘Dd-Pd(0)’’)and with unsupported palladium metal particles made by reduction under H2 (‘‘Chem-Pd(0)’’). Cell surface-located clusters of Pd(0) nanoparticles were detected on both D. desulfuricans and R. sphaeroides but the size and location of deposits differed among comparably loaded preparations.\ud \ud These differences may underlie the observation of different activities of Dd-Pd(0) and Rs-Pd(0) when compared with respect to their ability to promote hydrogen release from hypophosphite and to catalyze chloride release from chlorinated aromatic compounds. Dd-Pd(0) was more effective in the reductive dehalogenation of polychlorinated biphenyls (PCBs), whereas Rs-Pd(0) was more effective in the initial dehalogenation of pentachlorophenol (PCP) although the rate of chloride release from PCP was comparable with both preparations after 2 h

Alumina-supported Pd-Ag catalysts for low-temperature CO and methanol oxidation

Pd-Ag bimetallic catalysts, supported on gamma-Al2O3, have been evaluated as exhaust catalysts for methanol-fueled vehicles. Laboratory studies have shown that a 0.01% Pd-5% Ag catalyst has greater CO and CH3OH oxidation activity than either 0.01% Pd or 5% Ag catalysts alone. Moreover, Pd and Ag interact synergistically in the bimetallic catalyst to produce greater CO and CH3OH oxidation rates and lower yields of methanol partial oxidation products than expected from a mixture of the single-component catalysts. The Pd-Ag synergism results from Pd promoting the rate of O2 adsorption and reaction with CO and CH3OH on Ag. Rate enhancement by the bimetallic catalyst is greatest at short reactor residence times where the oxygen adsorption rate limits the overall reaction rate

Electron microscopy study of CeOx–Pd/α-Al2O3 catalysts for methane dry reforming

We have investigated the interaction between Pd and Ce in a 0.47 wt % CeOx–Pd 1 wt %/ -Al2O3 catalyst that is used in the reforming reaction of CH4 with CO2. The freshly reduced catalyst was characterized by various electron microscopy techniques, such as elemental mapping, Z-contrast imaging, and electron energy-loss spectroscopy to understand the role of Ce on a microscopic scale. The high spatial resolution elemental mapping indicates that CeOx is located in close proximity of the palladium nanoparticles. High-resolution lattice images and energy-loss spectra obtained in the vicinity of the Pd particles show an anisotropic distribution of CeOx crystallites limited to the interface region between Pd and the substrate but not covering the surface of the Pd nanoparticles. Energy-loss near edge fine structure of Pd M edges reveals that the Pd nanoparticles are not oxidized.Fil: Moreno, M. S.. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; ArgentinaFil: Wang, Feiya. National Institute for Nanotechnology; CanadáFil: Malac, M.. National Institute for Nanotechnology; CanadáFil: Kasama, T.. University of Cambridge; Reino UnidoFil: Gigola, Carlos Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Costilla, Ignacio Oscar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Sánchez, M. D.. Universidad Nacional del Sur. Departamento de Física; Argentin

Selective hydrogenation in trickle-bed reactor. Experimental and modelling including partial wetting.

A steady state model of a trickle bed reactor is developed for the consecutive hydrogenation of 1,5,9-cyclododecatriene on a Pd/Al2O3 catalyst. Various experiments have shown that the selectivity of this reaction towards the product of interest is much lower in co-current down-flow (trickle-bed) than in up-flow. This is due to uneven liquid distribution and to partial wetting of the catalyst surface at low liquid flow rates. The non-isothermal heterogeneous model proposed here takes into account the partial wetting of the catalyst, as well as the resistances to heat and mass transfer at the gas-liquid, liquid-solid and solid-gas interfaces. It assumes that the catalyst particles can be divided into two distinct concentration zones corresponding to the wetted and dry catalyst surfaces; mass transfer between these two zones is described by a simplified diffusion mechanism. Compared to previous models assuming a uniform concentration of liquid-phase components inside the catalyst particles, this model improves the prediction of the outlet concentrations of hydrogenation products