Lioubov Kiwi-Minsker

Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective?

The activity and selectivity of structure-sensitive reactions are strongly correlated with the shape and size of the nanocrystals present in a catalyst. This correlation can be exploited for rational catalyst design, especially if each type of surface atom displays a different behavior, to attain the highest activity and selectivity. In this work, uniform Pd nanocrystals with cubic (in two different sizes), octahedral, and cuboctahedral shapes were synthesized through a solution-phase method with poly(vinyl pyrrolidone) (PVP) serving as a stabilizer and then tested in the hydrogenation of 2-methyl-3-butyn-2-ol (MBY). The observed activity and selectivity suggested that two types of active sites were involved in the catalysis--those on the planes and at edges--which differ in their coordination numbers. Specifically, semihydrogenation of MBY to 2-methyl-3-buten-2-ol (MBE) occurred preferentially at the plane sites regardless of their crystallographic orientation, Pd(111) and/or Pd(100), whereas overhydrogenation occurred mainly at the edge sites. The experimental data can be fit with a kinetic modeling based on a two-site Langmuir-Hinshelwood mechanism. By considering surface statistics for nanocrystals with different shapes and sizes, the optimal catalyst in terms of productivity of the target product MBE was predicted to be cubes of roughly 3-5 nm in edge length. This study is an attempt to close the material and pressure gaps between model single-crystal surfaces tested under ultra-high-vacuum conditions and real catalytic systems, providing a powerful tool for rational catalyst design.

UV–Ozone Cleaning of Supported Poly(vinylpyrrolidone)-Stabilized Palladium Nanocubes: Effect of Stabilizer Removal on Morphology and Catalytic Behavior

Poly(vinylpyrrolidone) (PVP)-stabilized Pd nanocubes were synthesized, deposited on a carbon-based support, and subsequently treated with UV-ozone (UVO) in order to eliminate the traces of PVP still present on the surface. Cubes, being a thermodynamically unfavorable shape, are very prone to restructuring to minimize the interfacial free energy and thus allow the assessment of their morphological stability during UVO cleaning. The process of PVP removal was monitored by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and in situ attenuated total reflection infrared spectroscopy (ATR-IR). High-resolution scanning electron microscopy (SEM) imaging was used to evaluate the morphology of the nanocubes. The effect of PVP removal was also studied in the hydrogenation of acetylene, showing a 4-fold increase of activity. This method can be applied to nanoparticles of other common shapes, which expose different crystal planes, in order to study the structure sensitivity of chemical reactions.

Recent Advances in the Liquid‐Phase Synthesis of Metal Nanostructures with Controlled Shape and Size for Catalysis

Recent advances in the liquid‐phase synthesis of metal nanostructures of different sizes and shapes are reviewed regarding their catalytic properties. The controlled synthesis of nanostructures is based on the colloid chemistry techniques in the solution, which use organic nanoreactors and a variety of stabilizers. Their catalytic activity and selectivity depend on the particles shape and size, as shown for Suzuki and Heck coupling, hydrogenations, hydrogenolysis, oxidations, and electron‐transfer reactions. The knowledge of a reactions structure‐sensitivity relationship is important for the rational catalyst design in view of process intensification. Nanostructures can be used per se and in supported form to meet the requirements of an eventual process.

Pd/SiO2 catalysts: synthesis of Pd nanoparticles with the controlled size in mesoporous silicas

Synthesis of Pd nanoparticles with controlled size (d(Pd) = 1-3.6 nm) was carried out within the pores of the mesoporous HMS and SBA-15 silicas. Pd was ion-exchanged on non-calcined silicas, prepared by solvent extraction of the templates. A high concentration of silanol groups on the mesopore surface allowed attaining Pd loading up to 4.4. wt.%. The Pd/HMS and Pd/SBA-15 were characterised by chemical analysis, XRD, N2 adsorption-desorption and transmission electron microscopy (TEM) methods. The materials possess a high SSA and narrow pore size distribution. Introduction of Pd nanoparticles in HMS resulted in a progressive loss of the regularity in the mesoporous structure. On the contrary, all Pd/SBA-15 composites retained the original well-ordered 2D hexagonal structure of SBA-15. The thick walls of the SBA-15 framework are accounted for the higher stability observed. The TEM investigations confirmed that the Pd nanocrystals were located within the SBA-15 mesoporous framework channels. The particle size did not exceed the mesopore diameter (2-6 nm) at Pd loading of 0.1-4.4wt.%. Pd clusters were found to be resistant against sintering during air-calcination (550 degreesC, 4h). The catalyst 2.1%Pd/SBA-15 used in methane combustion at 520 degreesC demonstrated stable activity during 6h on stream.

Biphasic Hydrogenation over PVP Stabilized Rh Nanoparticles in Hydroxyl Functionalized Ionic Liquids

Polyvinyl pyrrolidone stabilized rhodium nanoparticles are highly soluble in hydroxyl-functionalized ionic liquids, providing an effective and highly stable catalytic system. In hydrogenation reactions, excellent results were obtained, and transmission electron microscopy, solubility determinations, and leaching experiments were employed to quantify the advantages of this catalytic system.

Structured combustion catalysts based on sintered metal fibre filters

Novel efficient structured combustion catalysts based on sintered metal fiber filters (MFF) were developed. To increase sp. surface area (SSA), metal fibers were coated by crack-free porous oxide films of SiO2, Al2O3, porous glass, and mesoporous SBA-15 silica. The composite materials presented uniform open macrostructure of the non-treated MFF filters and were suitable supports for deposition of catalytically active phases (Pd, Pt, and Co3O4). These catalysts were tested in hydrocarbon (CH4, C3H8) combustion. Co3O4 supported on MFF without any coating (6.8% Co3O4/MFF) was the most active for propane total oxidn. At the same time in methane combustion the activity of this catalyst was relatively low. Pd supported on the MFF coated by mesoporous SBA-15 film (0.5% Pd/SBA-15/MFF) demonstrated the highest activity in methane total oxidn. due to the high palladium dispersion. The SBA-15 film supported on MFF provided the highest dispersion of the deposited noble metals (Pd, Pt) with an av. particle size .apprx.2.0 nm. The metal nanoparticles formed within the mesopore channels were stable against sintering during calcination and the particle diam. was obsd. not to exceed the diam. of the silica pores. These catalysts did not undergo deactivation under reaction conditions at temps. up to 500 Deg. On the contrary, the Pd supported on MFF coated by the microporous SiO2 and Al2O3 films, prepd. by sol-gel technique, suffered from metal sintering during the calcination step and also during reaction, demonstrating strong catalyst deactivation. The catalytic filters are suitable materials for assembling different multiple layers to obtain structured catalytic beds with the compn./concn. gradients of active component in the axial direction. The enhanced overall catalytic performance was obsd. in adiabatic catalytic reactor during propane combustion due to a synergy of the 0.5% Pd/SBA-15/MFF and the 0.5% Pt/SBA-15/MFF catalytic layers assembled in the appropriate order forming gradient catalytic bed. [on SciFinder (R)]

Hydrogen production by catalytic cracking of methane over nickel gauze under periodic reactor operation

The catalytic cracking of methane over nickel gauze is proposed as an attractive alternative for the prodn. of CO-free hydrogen. The catalyst deactivates due to intensive coke deposition. Therefore, the reactor was operated periodically with the reaction followed by the catalyst regeneration by burning of coke in oxidative atm. The optimal reaction performance was found to consist of reaction periods of 4 min followed by 4 min regeneration periods. [on SciFinder (R)]

Three-phase nitrobenzene hydrogenation over supported glass fiber catalysts: reaction kinetics study

The catalytic properties of Pd and Pt supported on woven glass fibers (GF) were investigated in the three-phase hydrogenation of nitrobenzene (NB). Over all catalysts, a 100 % yield of aniline was attained. The catalytic activity for the best catalysts was two times higher than the activity of commercial Pt/C catalyst traditionally used for liquid‐phase hydrogenation. The intrinsic reaction kinetics were studied and a reaction scheme is suggested. The direct formation of aniline from NB was observed over Pd/ GF with traces of intermediates. Four intermediate products were detected during aniline formation over Pt/GF: nitrosobenzene, phenylhydroxylamine, azoxybenzene, and azobenzene. The Eley-Rideal kinetic model fits the experimental data well. The parameters of the model were determined as a function of initial NB concentration and hydrogen pressure. Pt and Pd supported on GF in woven fabrics are suggested as suitable materials for reactors with a structured catalytic bed in multiphase reactor performance.

Cloth catalysts for water denitrification II. Removal of nitrates using Pd-Cu supported on glass fibers

The use of glass fibers in the form of woven cloth (GFC), as a new type of catalytic support, was studied for the reduction of aqueous nitrate solutions using a Pd/Cu–GFC catalyst. The activity (per gram Pd) and selectivity to nitrogen were found to be comparable with those found for Pd–Cu catalysts supported on the other carriers. The maximal initial removal activity was found for a catalyst with a Pd/(Pd+Cu) ratio of 0.81. The corresponding activity was 0.7 mmol min-1 (gPd)-1, and the selectivity was 97 mol% at 25°C and pH 6.5 for initial nitrate concentration of 100 mg l-1. The selectivity to nitrogen declined at high conversions of nitrate and high pH.

Supported glass fibers catalysts for novel multi-phase reactor design

The catalytic properties of Pd and Pt supported on woven glass fabrics were explored for liquid-phase hydrogenation of benzaldehyde as a model for three-phase catalytic reaction. The catalysts demonstrated high activity and are suitable materials to be used in reactors with structured catalytic bed. The main characteristics of catalytic bed are discussed.