Brahim Mezari

Nucleation and Growth of Monodisperse Silica Nanoparticles

Although monodisperse amorphous silica nanoparticles have been widely investigated, their formation mechanism is still a topic of debate. Here, we demonstrate the formation of monodisperse nanoparticles from colloidally stabilized primary particles, which at a critical concentration undergo a concerted association process, concomitant with a morphological and structural collapse. The formed assemblies grow further by addition of primary particles onto their surface. The presented mechanism, consistent with previously reported observations, reconciles the different theories proposed to date.

Influence of Extraframework Aluminum on the Brønsted Acidity and Catalytic Reactivity of Faujasite Zeolite

A series of faujasite zeolites was modified by extraframework Al (AlEF) with the goal to investigate the influence of such species on the intrinsic Brønsted acidity and catalytic activity towards paraffin cracking. The chemical state of AlEF and zeolite acidity were investigated by 27Al MAS NMR and COads IR spectroscopy, H/D exchange reaction, and propane cracking. Strongly acidic defect‐free Y zeolites were obtained by substitution of framework Al by Si with (NH4)2SiF6. In accordance with the next‐nearest‐neighbor model, the intrinsic acidity of the protons increased with decreasing framework Al density. This increased acidity was evidenced by an increased shift of the OH stretching vibration upon CO adsorption in COads IR spectroscopy and by an increased H/D exchange rate in H/D exchange reactions with perdeuterobenzene. All of the acid sites in these zeolites were of equal strength beyond a certain Si/Al ratio. The increased acidity resulted in an enhanced propane cracking activity. Modification of a model dealuminated Y zeolite by AlEF only resulted in a small fraction of cationic AlEF species, because it was difficult to control the ion exchange process. In comparison, commercial ultrastabilized Y zeolites contained less AlEF and these species were predominantly present in cationic form. The rate of propane cracking strongly correlated to the concentration of Brønsted acid sites perturbed by cationic AlEF species. The results of MQMAS 27Al NMR spectroscopy confirmed the presence of sites perturbed by AlEF and unaffected framework Al sites. Zeolites with higher intrinsic cracking activities contained a higher proportion of perturbed sites. Although COads IR and H/D exchange methods proved to be suitable methods to probe the acidity of Y zeolites free from AlEF, they were less suitable to predict the reactivity if the Brønsted acid sites were affected by cationic AlEF species.

Synthesis of Sn-Beta with Exclusive and High Framework Sn Content

Sn‐Beta zeolite was prepared by acid dealumination of Beta zeolite, followed by dehydration and impregnation with anhydrous SnCl4. The formation of extraframework Sn (EFSn) species was prevented by the removal of unreacted SnCl4 in a methanol washing step prior to calcination. The resulting Sn‐Beta zeolites were characterized by X‐ray diffraction, Ar physisorption, NMR, UV/Vis, and FTIR spectroscopy. These well‐defined Lewis acid zeolites exhibit good catalytic activity and selectivity in the conversion of 1,3‐dihydroxyacetone to methyl lactate. Their performance is similar to a reference Sn‐Beta zeolite prepared by hydrothermal synthesis. Sn‐BEA zeolites that contain EFSn species exhibit lower catalytic activity; the EFSn species also catalyze formation of byproducts. DFT calculations show that partially hydrolyzed framework Sn‐OH species (open sites), rather than the tetrahedral framework Sn sites (closed sites), are the most likely candidate active sites for methyl lactate formation.

The formation of gigantic hollow silica spheres from an EO76–PO29–EO76/butanol/ethanol/H2O quaternary system

Gigantic hollow silica spheres with a hierarchical intra- and inter-particle porosity were obtained from an EO76–PO29–EO76/butanol/ethanol/H2O quaternary system, which is unique in its extremely rapid silica condensation and in the resulting hierarchical morphology.

Super-microporous organosilicas synthesized from well-defined nanobuilding units

Super-microporous organosilica with bridging ethylene and pendant vinyl groups has been synthesized by assembling predefined nanobuilding block polyhedral oligomeric silsesquioxanes (POSS) with nonionic surfactant Brij-76 as the template. The material shows wormhole-like super-micropores with uniform size of 1.9 nm, high BET surface area of 872 m2 g–1 and pore volume of 0.52 cm3 g–1. IR and NMR results show that the bridging ethylene, the pendant vinyl groups and the double-4-membered ring structure were successfully transferred from the building blocks to the super-microporous organosilica material. The material shows high hydrothermal stability and can further react with Br2. The advantage of the present approach lies in that the relative contents and proximity of the different organic functionalities in the final material can be well controlled through the starting nanobuilding blocks.

Molecular Promoting of Aluminum Metal–Organic Framework Topology MIL-101 by N,N-Dimethylformamide

In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.

The role of the amorphous phase in melting of linear UHMW-PE; implications for chain dynamics

In ultra-high molecular weight polyethylene (UHMW-PE), it is possible to obtain single chain forming single crystals, where chains are adjacently re-entrant. Depending on the heating rate, it is feasible to melt these crystals either by simple consecutive detachment of chain stems from the crystalline substrate or by cluster melting, where several chain stems are involved. The consecutive detachment of chain stems occurs at the melting point predicted from the Gibbs–Thomson equation, whereas the cluster melting at much higher temperatures. Melting by the consecutive detachment of chain stems from the crystal substrate and their diffusion in the melt ultimately result in a new melt state having a heterogeneous distribution of physical entanglements, which invokes differences in local mobility. With combined DSC, rheology and solid-state NMR studies, it is concluded that the disentangled domains present within the entangled matrix possess higher local mobility than the entangled domains, ultimately causing lower elastic modulus. The fraction of the entangled and disentangled domains is maintained at higher temperatures, leading to a thermodynamically non-equilibrium melt state. In contrast, in cluster melting, where several chain stems (initially disentangled) can simultaneously adopt the random coil state, entanglements that are formed are homogeneously distributed in the melt. The paper invokes the influence of the topological differences present in the amorphous phase of the semi-crystalline polymer on the melting kinetics of crystals. The reported findings have implications for the melting behaviour and the resulting melt state of polymers in general.

New Cu-Based Catalysts Supported on TiO2 Films for Ullmann SNAr-Type C-O Coupling Reactions

New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)).

One-Step Synthesis of Hierarchical ZSM-5 Using Cetyltrimethylammonium as Mesoporogen and Structure-Directing Agent

Hierarchical ZSM-5 zeolite is hydrothermally synthesized in a single step with cetyltrimethylammonium (CTA) hydroxide acting as mesoporogen and structure-directing agent. Essential to this synthesis is the replacement of NaOH with KOH. An in-depth solid-state NMR study reveals that, after early electrostatic interaction between condensed silica and the head group of CTA, ZSM-5 crystallizes around the structure-directing agent. The crucial aspect of using KOH instead of NaOH lies in the faster dissolution of silica, thereby providing sufficient nutrients for zeolite nucleation. The hierarchical ZSM-5 zeolite contains mesopores and shows excellent catalytic performance in the methanol-to-hydrocarbons reaction.

Competitive Adsorption of Substrate and Solvent in Sn-Beta Zeolite During Sugar Isomerization

Abstract The isomerization of 1,3‐dihydroxyactone and d‐glucose over Sn‐Beta zeolite was investigated by in situ 13C NMR spectroscopy. The conversion rate at room temperature is higher when the zeolite is dehydrated before exposure to the aqueous sugar solution. Mass transfer limitations in the zeolite micropores were excluded by comparing Sn‐Beta samples with different crystal sizes. Periodic density functional theory (DFT) calculations show that sugar and water molecules compete for adsorption on the active framework Sn centers. Careful solvent selection may thus increase the rate of sugar isomerization. Consistent with this prediction, batch catalytic experiments show that the use of a co‐solvent, such as tetrahydrofuran, that strongly interacts with the Sn centers suppresses glucose isomerization. On the other hand, the use of ethanol as cosolvent results in significantly higher isomerization activity in comparison with pure water because of decreased competition with glucose adsorption on zeolitic Sn sites.