27 research outputs found
Solvent-free semihydrogenation of acetylene alcohols in a capillary reactor coated with a Pd-Bi/TiO2 catalyst
© 2016 Elsevier B.V. All rights reserved. A solvent-free semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol was performed in a capillary reactor (10 m long, 0.53 mm i.d.) coated with a titania supported Pd-Bi catalyst. Several coatings with different Pd/Bi ratio have been prepared. The catalysts have been characterized with SEM, TEM, EDX, XRD analysis and N 2 adsorption-desorption measurements. The maximum alkene yield of 90% was obtained at a molar Pd/Bi ratio of 11. The yield was increased to 95% in the presence of 10 mol.% pyridine in the reaction mixture. The alkene selectivity decreased with time due to leaching of Bi. The leaching was fully suppressed in the presence of 1 vol.% acetic acid in the reaction mixture. The catalyst remained stable for 100 h of continuous operation. The results demonstrate that capillary reactors provide alkene selectivity the same compared to ideal stirred tank batch reactors
Scale up study of capillary microreactors in solvent-free semihydrogenation of 2âmethylâ3âbutynâ2âol
A 2.5 wt.% Pd/ZnO catalytic coating has been deposited onto the inner wall of capillary reactors with a diameter of 0.53 and 1.6 mm. The coatings were characterised by XRD, SEM, TEM and elemental analysis. The performance of catalytic reactors was studied in solvent-free hydrogenation of 2-methyl-3-butyn-2-ol. No mass transfer limitations was observed in the reactor with a diameter of 0.53 mm up to a catalyst loading of 1.0 kg (Pd) m â3 . The activity and selectivity of the catalysts has been studied in a batch reactor to develop a kinetic model. The kinetic model was combined with the reactor model to describe the obtained data in a wide range of reaction conditions. The model was applied to calculate the range of reaction conditions to reach a production rate of liquid product of 10â50 kg a day in a single catalytic capillary reactor
Palladium-bismuth intermetallic and surface-poisoned catalysts for the semi-hydrogenation of 2-methyl-3-butyn-2-ol
The effects of poisoning of Pd catalysts with Bi and annealing in a polyol (ethylene glycol) were studied on the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY). An increase in the Pd:Bi ratio from 7 to 1 in the Bi-poisoned catalysts decreased the hydrogenation activity due to blocking of active sites, but increased maximum alkene yield from 91.5% for the Pd catalyst to 94â96% for all Bi-poisoned Pd catalysts, by decreasing the adsorption energy of alkene molecules and suppressing the formation of ÎČ-hydride phase. Annealing of the catalysts induced the formation of intermetallic phases and decreased its activity due to sintering of the catalytic particles and low activity of intermetallic compounds. LangmuirâHinshelwood kinetic modelling of the experimental data showed that poisoning of Pd with Bi changed the relative adsorption constants of organic species suggesting ligand effects at high Bi content
Nanoparticulate Pd-Sn Compounds Supported on Metal Oxides: Synthesis, Material and Catalytic Properties
The manufacture of chemicals requires innovation at the catalyst frontier so that processes can be developed with higher energy efficiency and increased facility of separation and recovery of products. Catalysts with high selectivity and activity control the overall efficiency of a process by avoiding unwanted side-reactions and increasing the conversion per unit time. Although processes catalysed by homogeneous catalysts have the advantage of offering better control and understanding of the reaction mechanism, their frequent dependence on expensive metals which are difficult to recover, often precludes their employment in large-scale applications. Heterogeneously catalysed reactions on the other hand, are not associated with problems regarding recycling and reuse of catalyst, contamination of products or intermediates. This work reports the synthesis, characterization and testing of Pd-Sn nanoalloy catalyst in the selective hydrogenation of 2-methyl-3-butyn-2-ol. Our results show that the Pd-Sn nanoalloy, of composition Pd2.8Sn, supported on ZnO (Pd2.8Sn/ZnO), offers very high activity and selectivity in the semi-hydrogenation of 2-methyl-3-butyn-2-ol to 2-methyl-3-buten-2-ol in the liquid phase. Under identical reaction conditions, Pd2.8Sn/ZnO shows activity, both turnover frequency and activity normalized by Pd content, significantly higher than Pd/CaCO3 (the Lindlar catalyst), with TOF of 137.6 sâ1 compared to 79.2 sâ1 for Pd/CaCO3 with approximately equal selectivity. The preparation of Pd2.8Sn/ZnO is achieved using a one-pot polyol procedure with the addition of a capping agent (polyvinylpyrrolidone) to control the particle size distribution. TEM shows nanoparticles evenly dispersed on the support, with a size distribution of 4.06 ± 0.75 nm. Single phase Pd2.8Sn was also prepared without the ZnO support, via the polyol method. Powder X-Ray diffraction data from the unsupported nanoalloy shows that the unit cell of Pd2.8Sn is face centred cubic with the Pd and Sn atoms occupying randomly the same crystallographic position. The chemical formula was calculated from a combination of ICP and PXRD analyses
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
Enhanced Wastewater Remediation Using Mesoporous Activated Wheat Straw Biochars: A Dye Removal Perspective
The escalating contamination of water bodies by synthetic dyes necessitates innovative and ecoconscious strategies for wastewater treatment. In this study, activated biochars BC-800 (1:0.25), BC-800 (1:0.5), and BC-800 (1:1) from wheat straw were synthesized. Here, ratios denote the mass relationship between wheat straw and potassium hydroxide; â800â represents the pyrolysis temperature. These activated biochars were rigorously characterized revealing the most efficient material, BC-800 (1:1), presenting a surface area of 2578.82 m2/g and average pore diameter of 5.51 nm. Across parallel batch experiments, it effectively extracted synthetic dyes (rhodamine B (RhB), methylene blue (MB), and methyl orange (MO)) from wastewater within 15â20 min, primarily through chemisorption pathways. Increased surface area and porosity resulted in a greater dispersion of adsorption sites including CâC linkages (ÏâÏ interactions) and H-bonding via surface carbonyl groups (CâO). To understand the adsorption mechanism, Langmuir, Freundlich, and Temkin isotherm models were employed to investigate the equilibrium adsorption behavior. Results show that BC-800 (1:1) followed the Freundlich isotherm (R2: 0.9659 for RhB, 0.9927 for MB, and 0.9979 for MO, respectively), showing dye molecules form multilayers on the surface of the biochar (Ï-stacking). Biochar recycling through chemical regeneration demonstrated sustained dye removal efficiency >90% for BC-800 (1:1) over multiple cycles
Stabilization of Pd3âxIn1+x polymorphs with Pd-like crystal structure and their superior performance as catalysts for semi-hydrogenation of alkynes
Selective hydrogenation (semi-hydrogenation) reactions of alkynes rely on Pd-based catalysts to provide the correct pathway to favour formation of double bonds and avoid full hydrogenation to single bonds. Here, we present the preparation and characterisation of "Pd3In"/TiO2 nanocatalysts, which show improved activity and selectivity compared to pure Pd catalysts, towards the liquid phase semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE), a fundamental step in the preparation of pharmaceuticals, and other industrially produced substances, as well as a model reaction for the semi-hydrogenation of alkynes. For both the supported and unsupported "Pd3In" alloys (later redefined as Pd3-xIn1+x), we stabilised two new cubic polymorphs with a Pd-like structure, instead of the tetragonal structure as reported so far in the literature. The stabilisation of these new polymorphs was made possible by using a solution-based synthesis and, thanks to the use of different solvents, the reaction was 2 carried out at different temperatures and the Pd/In ratio could be tuned. The same synthetic approach was adapted to prepare two "Pd3In"/TiO2 catalysts by adding the TiO2 support to the reaction mixture, in a practical one-step, one-pot reaction. HREM and X-Ray maps show that the cubic crystal structure of "Pd3In" is maintained when prepared in the presence of the support, however, the support seems to influence the Pd/In ratio
Bi2WO6/C-dots/TiO2: A novel z-scheme photocatalyst for the degradation of fluoroquinolone levofloxacin from aqueous medium
© 2020 by the authors. Licensee MDPI, Basel, Switzerland. Photocatalytic materials and semiconductors of appropriate structural and morphological architectures as well as energy band gaps are materials needed for mitigating current environmental problems, as these materials have the ability to exploit the full spectrum of solar light in several applications. Thus, constructing a Z-scheme heterojunction is an ideal approach to overcoming the limitations of a single component or traditional heterogeneous catalysts for the competent removal of organic chemicals present in wastewater, to mention just one of the areas of application. A Z-scheme catalyst possesses many attributes, including enhanced light-harvesting capacity, strong redox ability and different oxidation and reduction positions. In the present work, a novel ternary Z-scheme photocatalyst, i.e., Bi2WO6/C-dots/TiO2, has been prepared by a facile chemical wet technique. The prepared solar light-driven Z-scheme composite was characterized by many analytical and spectroscopic practices, including powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), N2 adsorptionâdesorption isotherm, Fourier-transform infrared spectroscopy (FT-IR), photoluminescence (PL) and UV-vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of the Bi2WO6/C-dots/TiO2 composite was evaluated by studying the degradation of fluoroquinolone drug, levofloxacin under solar light irradiation. Almost complete (99%) decomposition of the levofloxacin drug was observed in 90 min of sunlight irradiation. The effect of catalyst loading, initial substrate concentration and pH of the reaction was also optimized. The photocatalytic activity of the prepared catalyst was also compared with that of bare Bi2WO6, TiO2 and TiO2/C-dots under optimized conditions. Scavenger radical trap studies and terephthalic acid (TPA) fluorescence technique were done to understand the role of the photo-induced active radical ions that witnessed the decomposition of levofloxacin. Based on these studies, the plausible degradation trail of levofloxacin was proposed and was further supported by LC-MS analysis
PdâSn nanoparticles on TiOâ and ZnO supports as catalysts for semi-hydrogenation : synthesis and catalytic performance
The two catalysts PdâSn/TiOâand Pd3Sn/ZnO were prepared via a one-pot procedure based on the âpolyol methodâ with the addition of a capping agent (polyvinylpyrrolidone) to control the particle size distribution. The same procedure was used to prepare Pd/TiO2 and Pd/ZnO for comparison. All four catalysts showed high activity and selectivity for the selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) in the liquid phase under identical conditions. However, PdâSn/TiOâand PdâSn/ZnO show selectivities to alkene significantly higher than that of the Pd catalysts. Specifically, the selectivity increases from 96.4% to 97.4% on TiOâsupport, and 96.2% to 97.6% on ZnO support, at 90% conversion. Transition electron microscopy shows nanoparticles evenly dispersed on the support, with mean particle sizes as low as 4.1 (±0.8) nm when Sn is incorporated into the catalyst. Unsupported Pd3Sn was prepared using the same method and characterised by powder X-Ray diffraction followed by the Rietveld refinement. Pd3Sn was found to be single-phase and isostructural to Pd metal with a face centred cubic unit cell