ABSTRACT
Complex nanomaterials produced by scale-up batch processes lack suitable control of shape, size distribution, chemical composition, and quality, because heat and mass transfer are seriously affected as the reactor volume increases. Here we use a novel continuous synthesis procedure, the active gas-liquid segmented flow, to produce noble metal-magnetic heteronanostructures with enormous interest in the fields of catalysis, biomedicine, environmental sensors, food monitoring, and chemical analysis. The microreactor technology proposed scales down the reaction volume to gain advantage of the large surface area to volume ratio with respect to conventional batch-type reactors, improving heat and mass transport and, consequently, promoting a uniform heating and mixing. The gas phase was introduced in the chemical reactor as gas slugs of nanoliter scale with a dual role: (1) passive mixing and (2) chemical directing agent to tune the crystallization of nanostructures in a continuous fashion. The shape, size, and magnetic properties of the resulting heteronanostructures, as well as the density, size, and composition of noble metal nanoparticles were tuned to show the versatility of the proposed approach in a timeline of 4 min. We demonstrated that the produced nanostructures provide excellent catalytic properties in the catalyzed hydrogenation of nitrophenols to aminophenols. Electron microscopy, UV-vis spectroscopy, and cyclic voltammetry studies showed the remarkable catalytic performance of the produced heteronanostructures.
ABSTRACT
Polymeric ionic liquids (PILs) have triggered great interest as all solid-state flexible electrolytes because of safety and superior thermal, chemical, and electrochemical stability. It is of great importance to fabricate highly conductive electrolyte membranes capable to operate above 120 °C under anhydrous conditions and in the absence of mineral acids, without sacrificing the mechanical behavior. Herein, the diminished dimensional and mechanical stability of poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide has been improved thanks to its infiltration on a polybenzimidale (PBI) support with specific pore architecture. Our innovative solution is based on the synergic combination of an emerging class of materials and sustainable large-scale manufacturing techniques (UV polymerization and replication by microtransfer-molding). Following this approach, the PIL plays the proton conduction role, and the PBI microsieve (SPBI) mainly provides the mechanical reinforcement. Among the resulting electrolyte membranes, conductivity values above 50 mS·cm-1 at 200 °C and 10.0 MPa as tensile stress are shown by straight microchannels of poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide cross-linked with 1% of dyvinylbenzene embedded in a PBI microsieve with well-defined porosity (36%) and pore diameter (17 µm).
ABSTRACT
In this work we investigate the formation of PtAu monodisperse alloyed nanoparticles by ageing pure metallic Au and Pt small nanoparticles (sNPs), nanoparticle size <5 nm, under certain conditions. We demonstrate that those bimetallic entities can be obtained by controlling the size of the initial metallic sNPs separately prepared and by selecting their appropriate capping agents. The formation of this spontaneous phenomenon was studied using HR-STEM, EDS, ionic conductivity, UV-Vis spectroscopy and cyclic voltammetry. Depending on the type of capping agent used and the size of the initial Au sNPs, three different materials were obtained: (i) AuPt bimetallic sNPs showing a surface rich in Au atoms, (ii) segregated Au and Pt sNPs and (iii) a mixture of bimetallic nanoparticles as well as Pt sNPs and Au NPs. Surface segregation energies and the nature of the reaction environment are the driving forces to direct the distribution of atoms in the bimetallic sNPs. PtAu alloyed nanoparticles were obtained after 150 h of reaction at room temperature if a weak capping agent was used for the stabilization of the nanoparticles. It was also found that Au atoms diffuse towards Pt sNPs, producing a surface enriched in Au atoms. This study shows that even pure nanoparticles are prone to be modified by the surrounding nanoparticles to give rise to new nanomaterials if atomic diffusion is feasible.
