Reyes Mallada

Porous membranes from acid decorated block copolymer nano-objects via RAFT alcoholic dispersion polymerization

The RAFT dispersion polymerization of methyl methacrylate (MMA) was conducted in ethanol at 70 °C using a poly(methacrylic acid) (PMAA) chain transfer agent. The poly(methacrylic acid) block is soluble in ethanol and acts as a steric stabilizer for the growing insoluble PMMA chains, resulting in the in situ formation of diblock copolymer nano-objects (Polymerization Induced Self-Assembly (PISA)) in the form of spheres, worms or vesicles, depending on the precise reaction conditions as judged by transmission electron microscopy and dynamic light scattering studies. Two detailed phase diagrams using PMAA27 and PMAA47 macro-CTAs were constructed as a road map for the synthesis of pure morphologies. It was observed that the pure phases could be obtained using the longer macro-CTA while the pure worm phase was not observed with the shorter PMAA. Spin-coated thin films of the prepared spherical particles exhibited a connected porous network as evaluated by electron microscopy (SEM, TEM). Finally, the prepared porous thin film was tested as an isoporous membrane for water filtration.

A Nanoarchitecture Based on Silver and Copper Oxide with an Exceptional Response in the Chlorine-Promoted Epoxidation of Ethylene

The selective oxidation of ethylene to ethylene epoxide is highly challenging as a result of competing reaction pathways leading to the deep oxidation of both ethylene and ethylene oxide. Herein we present a novel catalyst based on silver and copper oxide with an excellent response in the selective oxidation pathway towards ethylene epoxide. The catalyst is composed of different silver nanostructures dispersed on a tubular copper oxide matrix. This type of hybrid nanoarchitecture seems to facilitate the accommodation of chlorine promoters, leading to high yields at low reaction temperatures. The stability after the addition of chlorine promoters implies a substantial improvement over the industrial practice: a single pretreatment step at ambient pressure suffices in contrast with the common practice of continuously feeding organochlorinated precursors during the reaction.

Continuous production of iron-based nanocrystals by laser pyrolysis. Effect of operating variables on size, composition and magnetic response.

Well dispersed iron-based magnetic nanoparticles have been prepared by gas phase laser-driven decomposition of iron pentacarbonyl. Agglomeration of the newly synthesized nanoparticles could be avoided by using a liquid collection system in which the exit stream from the laser reactor was bubbled through triethylene glycol (TREG). The effect of different experimental parameters (precursor concentration, laser power, working pressure, residence time) was studied and, by selecting the appropriate conditions, the size of the resulting magnetic nanocrystals could be tuned from ultrasmall (ca.xa02.5xa0nm) to around 12xa0nm. For nanoparticle sizes around 10xa0nm and larger a metallic iron core could be preserved. These iron/iron oxide core-shell compositions exhibit very high values of magnetization, 127xa0emuxa0g(-1).

Nano-structured magneto-responsive membranes from block copolymers and iron oxide nanoparticles

Mixed matrix membranes (MMMs) provide an exciting alternative to traditional membranes due to their favorable properties from both building blocks which are essential for certain separation applications. Block copolymer directed synthesis of MMMs is an innovative approach for the preparation of porous materials. In the current work the syntheses of mixed matrix membranes from a PMAA-b-PMMA block copolymer and functionalized iron oxide magnetic nanoparticles are demonstrated. The block copolymers were synthesized using a RAFT polymerization technique, along with three different types of magnetic nanoparticles with various surface properties. The thin film membranes were prepared by mixing different ratios of diblock copolymer in THF and iron oxide nanoparticles in water followed by tape casting or spin coating. The particles and the membranes were characterized using TEM, DLS, and SEM. The permeation behavior of the membranes was assessed using filtration tests in the presence and absence of a magnetic field.

Microwave-Assisted Catalytic Combustion for the Efficient Continuous Cleaning of VOC-Containing Air Streams

A microwave-heated adsorbent-reactor system has been used for the continuous cleaning of air streams containing n-hexane at low concentrations. Both, a single catalytic bed (PtY zeolite) and a double (adsorptive DAY zeolite + catalytic PtY zeolite) fixed-bed reactor configurations were studied under dry and humid conditions. The zeolites were selectively heated by short periodic microwave pulses that caused the desorption of n-hexane and its subsequent catalytic combustion. The double bed configuration was attractive because it allowed nearly the same performance with only half of the catalyst load. The operation was especially efficient under realistic humid gas conditions that favored more intense microwave absorption, producing a faster heating of the adsorptive and catalytic beds. Under these conditions, continuous gas cleaning could be achieved with short (3 min, 30 W) microwave heating pulses every 5 min.

Development of fluorescent thermoresponsive nanoparticles for temperature monitoring on membrane surfaces

In this work, tris(phenantroline)ruthenium(II) chloride (Ru(phen)3) was immobilized in silica nanoparticles prepared according to the Stöber method. Efforts were devoted on the optimization of the nano-thermometer in terms of size, polydispersity, intensity of the emission and temperature sensitivity. In particular, the immobilization of the luminophore in an external thin shell made of silica grown in a second step on bare silica nanoparticles allowed producing fluorescent monodisperse silica nanoparticles (420±20nm). A systematic study was addressed to maximize the intensity of the emission of the fluorescent nanoparticles by adjusting the concentration of Ru(phen)32+ in the shell from 0.2 to 24wt.%, whereas the thickness of the shell is affected by the amount of silica precursor employed. The luminescent activity of the doped nanoparticles was found to be sensitive to the temperature. In fact, the intensity of the emission linearly decreased by increasing the temperature from 20°C to 65°C. The thermoresponsive nanoparticles were functionalized with long aliphatic chains in order to obtain hydrophobic nanoparticles. The developed nanoparticles were immobilized via dip-coating procedure on the surface of hydrophobic porous membranes, such as Polyvinylidene fluoride (PVDF) prepared via Non-Solvent Induced Phase Separation (NIPS), providing local information about the membrane surface temperature.

Exploring the Gas-Permeation Properties of Proton-Conducting Membranes Based on Protic Imidazolium Ionic Liquids: Application in Natural Gas Processing

This experimental study explores the potential of supported ionic liquid membranes (SILMs) based on protic imidazolium ionic liquids (ILs) and randomly nanoporous polybenzimidazole (PBI) supports for CH4/N2 separation. In particular, three classes of SILMs have been prepared by the infiltration of porous PBI membranes with different protic moieties: 1-H-3-methylimidazolium bis (trifluoromethane sulfonyl)imide; 1-H-3-vinylimidazolium bis(trifluoromethane sulfonyl)imide followed by in situ ultraviolet (UV) polymerization to poly[1-(3H-imidazolium)ethylene] bis(trifluoromethanesulfonyl)imide. The polymerization process has been monitored by Fourier transform infrared (FTIR) spectroscopy and the concentration of the protic entities in the SILMs has been evaluated by thermogravimetric analysis (TGA). Single gas permeability values of N2 and CH4 at 313 K, 333 K and 363 K were obtained from a series of experiments conducted in a batch gas permeance system. The results obtained were assessed in terms of the preferential cavity formation and favorable solvation of methane in the apolar domains of the protic ionic network. The most attractive behavior exhibited poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide polymeric ionic liquid (PIL) cross-linked with 1% divinylbenzene supported membranes, showing stable performance when increasing the upstream pressure. The CH4/N2 permselectivity value of 2.1 with CH4 permeability of 156 Barrer at 363 K suggests that the transport mechanism of the as-prepared SILMs is solubility-dominated.

Laser-Assisted Production of Carbon-Encapsulated Pt-Co Alloy Nanoparticles for Preferential Oxidation of Carbon Monoxide

C-encapsulated highly pure PtxCoy alloy nanoparticles have been synthesized by an innovative one-step in-situ laser pyrolysis. The obtained X-ray diffraction pattern and transmission electron microscopy images correspond to PtxCoy alloy nanoparticles with average diameters of 2.4 nm and well-established crystalline structure. The synthesized PtxCoy/C catalyst containing 1.5 wt% of PtxCoy nanoparticles can achieve complete CO conversion in the temperature range 125–175°C working at weight hourly space velocities (WHSV) of 30 L h−1g−1. This study shows the first example of bimetallic nanoalloys synthesized by laser pyrolysis and paves the way for a wide variety of potential applications and metal combinations.