Joumana Toufaily

Synthesis of purely silica MFI-type nanosheets for molecular decontamination

Conventional syntheses of zeolites generally lead to the formation of crystals whose sizes are of the order of several microns which is not detrimental in a large number of industrial applications. However, the capacity and kinetics of pollutant adsorption which are sensitive to diffusion phenomena, surface and porous volume could potentially be improved by the use of nanocrystal or hierarchical zeolites (micro/mesoporous or micro/macroporous). Indeed, zeosil nanosheets hold great potential because of their small size and their high porous volume that promote access of pollutants and increase the adsorption capacity. Herein, silicalite-1 zeosil with a lamellar morphology was successfully synthesized under hydrothermal conditions (110 °C, 10 days) using diquaternary ammonium as structuring agent. Compared to the conventional silicalite-1 material, the porous volume of the synthesized nanosheets determined from the N2 adsorption–desorption isotherms was found to be multiplied by 3.5 (0.62 cm3 g−1) without altering the microporous volume (0.18 cm3 g−1). This result was also confirmed by the increase of the n-hexane adsorption capacity and kinetics in the silicalite-1 nanosheets compared to the conventional silicalite-1. This approach indicates a new way for obtaining zeosil materials of controlled sizes and shapes for molecular decontamination.

Copper photoredox catalysts for polymerization upon near UV or visible light: structure/reactivity/efficiency relationships and use in LED projector 3D printing resins

Copper complexes (CuCs) bearing pyridine–pyrazole ligands are synthesized and evaluated as new photoredox catalysts/photoinitiators in combination with an iodonium salt (Iod) for the free radical polymerization of (meth)acrylates and the cationic polymerization of epoxides upon visible light exposure using a Light Emitting Diode (LED)@405 nm. The structure/reactivity/efficiency relationships for the copper complexes are studied as well as the chemical mechanisms involved. The different substituents on the pyrazole moiety of the ligand allow tuning of the oxidation potential and the visible light absorbance of the complexes and to optimize the performance of the polymerization photoredox catalysts. The use of a novel additive (CARET) in a three-component system (CuC/Iod/CARET) highly improves the performance. Finally, the high performances of the Cu(I) complexes for the development of new 3D printing resins using an LED projector are demonstrated. Currently, LED projector printing is really advantageous in 3D printing i.e. this technology projects the profile of an entire layer at one time.

Photoinitiating systems of polymerization and in situ incorporation of metal nanoparticles into polymer matrices upon exposure to visible light: push–pull malonate and malononitrile based dyes

Novel push–pull dyes containing a (substituted) hydrocarbon moiety and a malonate (or a malononitrile) moiety are proposed as photoinitiators for the ring opening polymerization of epoxides as well as the synthesis of interpenetrated polymer networks (IPNs) upon exposure to visible light (laser diode, halogen lamp, etc.). Excellent polymerization profiles are obtained. The role of the acceptor and donor moieties in these dyes towards their light absorption properties, the associated photochemical processes and their photoinitiating ability is investigated. A very efficient dye has been selected for the reduction of Ag+ and the in situ formation of Ag(0) nanoparticles in the synthesized IPNs.

Adsorption kinetics and equilibrium of phenol drifts on three zeolites

In this study, the sorption of phenol drifts was studied by performing batch kinetic sorption experiments. The equilibrium kinetic data was analyzed using the pseudo-second-order kinetic model. Fowler-Guggenheim model gives a perfect fitting with the isotherm data. The influence of porous structure of a zeolite particle on phenol adsorption from aqueous solutions is analyzed and discussed. The adsorption for phenol drifts on zeolite was proved to be an exothermic process. Thus the solubility of the phenolic compound and the pH of the solution play also an important role in adsorption phenomena.The relative affinity of the phenolic compound toward the zeolite was related to the electron donor-acceptor complexes that were formed between the basic sites on the zeolite (oxygen) and hydrogens (acidic site) of the phenols. Finally zeolite seems to be an efficient adsorbent; it can be easily regenerated by methanol leaching.

Immobilization of TiO2 nanoparticles on natural Luffa cylindrica fibers for photocatalytic applications

TiO2/Luffa composites have been successfully prepared via a sol–gel method from the hydrolysis of a precursor of TiO2. The possibility to use Luffa fibers as biotemplate to self-support hierarchical TiO2 macrostructures has also been tested with success. The photocatalysts and the TiO2/Luffa composites were characterized by X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, FT-IR, and UV-visible spectroscopy. The photocatalytic activities have been investigated in the photodegradation of methanol, chosen as model molecules for VOCs in air. The reactions have been followed by IR-operando spectroscopy. TiO2/Luffa composites exhibited a good stability and photocatalytic activity under UV light irradiation, giving rise to a new generation of green photocatalysts, easy to shape and manufacture, for the photodegradation of organic pollutants.

The application of titanium dioxide, zinc oxide, fullerene, and graphene nanoparticles in photodynamic therapy

Nanoparticles (NPs) have been shown to have good ability to improve the targeting and delivery of therapeutics. In the field of photodynamic therapy (PDT), this targeting advantage of NPs could help ensure drug delivery at specific sites. Among the commonly reported NPs for PDT applications, NPs from zinc oxide, titanium dioxide, and fullerene are commonly reported. In addition, graphene has also been reported to be used as NPs albeit being relatively new to this field. In this context, the present review is organized by these different NPs and contains numerous research works related to PDT applications. The effectiveness of these NPs for PDT is discussed in detail by collecting all essential information described in the literature. The information thus assembled could be useful in designing new NPs specific for PDT and/or PTT applications in the future.

Functionalization of SBA-15 materials for the adsorption of phenols from aqueous solution

Water pollution by toxic organic compounds is a problem and demand for efficient adsorbents for the removal of toxic compounds is increasing. In the present work, we studied the functionalization of SBA-15 materials via the co-condensation between an alkoxysilane and an organoalkoxysilane in the presence of P123 as structuring agent. Several types of ligands were used: 3-mercaptopropylmethyldimethoxysilane, N-[3-(trimethoxysilyl) propyl] aniline; aminopropyltrimethoxysilane; [aminoethylamino]-propyltrimethoxysilanes and [(2-aminoethylamino) ethylamino] propyltrimethoxysilanes. These materials exhibit BET surface area of 275–776 m2/g and total pore volume of 0.29–1 cm3/g, depending on the ligand types and contents. Elementary analysis results confirm the incorporation of both thiol and amine group in the materials. Batch adsorption studies shows that the adsorption capacity of phenol drifts on the amine and thiol functionalized SBA-15 is greater than that on pure SBA-15. A linear relationship was observed between the adsorption capacity and N/SiO2 ratio. It was shown that the presence of amine promotes interactions with water molecules, on the other hand, these results can also be explained by the basic behavior of N-functionalized materials.

Surface modification of TiO2 nanoparticles with AHAPS aminosilane: distinction between physisorption and chemisorption

This paper addresses the surface modification of TiO2 nanoparticles with n-(6-aminohexyl)aminopropyltrimethoxysilane (AHAPS) using various initial aminosilane concentrations. The main objective of this article is to show experimentally the importance of the physisorption during the grafting process. The distinction between chemisorbed and physisorbed aminosilane molecules on TiO2 is thoroughly analyzed. The surface of bare and modified TiO2 particles has been characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) to gain a better understanding of the adsorption mechanism of AHAPS on TiO2. Quantitative information on surface energy of TiO2, in terms of adsorption energy sites and heterogeneity, has been investigated by quasi-equilibrium low-pressure adsorption technique using nitrogen and argon as probe molecules. The FTIR and XPS data are combined to estimate and discuss the chemisorbed and physisorbed contribution. The results demonstrate that both physisorption and chemisorption occurs but they display a different behavior. The physisorbed amounts are much higher than the chemisorbed amounts. This shows that the main part of the adsorbed layer is composed of physisorbed molecules. The physisorbed uptake depends highly on the AHAPS concentration while the chemisorbed amount remains constant. Quasi-equilibrium Ar derivative adsorption isotherms reveal that the AHAPS molecules are mostly located on the {101} and {001} faces of titania and that the two faces display the same reactivity toward AHAPS sorption. Nitrogen adsorption experiments show that the sorption takes place on the three polar surface sites of high energy. The molecules are chemisorbed onto the site displaying the highest energy while they are physisorbed on the two lower energy sites.

Efficient synthetic access to thermo-responsive core/shell nanoparticles

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe3O4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe3O4/polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

Novel Carbazole Skeleton-Based Photoinitiators for LED Polymerization and LED Projector 3D Printing

Radical chemistry is a very convenient way to produce polymer materials. Here, an application of a particular photoinduced radical chemistry is illustrated. Seven new carbazole derivatives Cd1–Cd7 are incorporated and proposed as high performance near-UV photoinitiators for both the free radical polymerization (FRP) of (meth)acrylates and the cationic polymerization (CP) of epoxides utilizing Light Emitting Diodes LEDs @405 nm. Excellent polymerization-initiating abilities are found and high final reactive function conversions are obtained. Interestingly, these new derivatives display much better near-UV polymerization-initiating abilities compared to a reference UV absorbing carbazole (CARET 9H-carbazole-9-ethanol) demonstrating that the new substituents have good ability to red shift the absorption of the proposed photoinitiators. All the more strikingly, in combination with iodonium salt, Cd1–Cd7 are likewise preferred as cationic photoinitiators over the notable photoinitiator bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO) for mild irradiation conditions featuring their remarkable reactivity. In particular their utilization in the preparation of new cationic resins for LED projector 3D printing is envisioned. A full picture of the included photochemical mechanisms is given.