RESUMEN
We developed synthetic methods for the doping of metals (M) with metallic nanoparticles (NPs). To the best of our knowledge - unlike oxides, polymers and carbon-based supports - metals were not used so far as supporting matrices for metallic NPs. The composites (denoted M1-NPs@M2) comprise two separate phases: the metallic NPs (the dopant) and the entrapping 3D porous metallic matrix, within which the NPs are intimately held and well dispersed. Two different general synthetic strategies were developed, each resulting in a group of materials with characteristic structure and properties. The first strategy uses pre-prepared NPs and these are entrapped during reductive formation of the metallic matrix from its cation. The second strategy is in situ growth of the doped metallic NPs within the pre-prepared entrapping metallic matrix. These two methods were developed for two types of entrapping metallic matrices with different morphologies: porous aggregated metallic matrices and metallic foams. The leading case in this study was the use of Pt as the NP dopant and Ag as the entrapping matrix, using all of the four combinations - entrapment or growth within aggregated Ag or Ag foam matrices. Full physical and chemical properties analysis of these novel types of materials was carried out, using a wide variety of analytical methods. The generality of the methods developed for these bi-metallic composites was investigated and demonstrated on additional metallic pairs: Au NPs within Ag matrices, Pd NPs within Ni matrices and Ir-NPs within a Rh matrix. As the main application of metallic NPs is in catalysis, the catalytic activity of M1-NPs@M2 is demonstrated successfully for entrapped Pt within Ag for reductive catalytic reactions, and for Pd within Ni for the electrocatalytic hydrogen oxidation reaction.
RESUMEN
A successful methodology for obtaining hybrid films which allow thermal triggering and continuous, irreversible, control of their hydrophilicity/hydrophobicity nature was developed. Two types of poly(dimethylsiloxane)-silica (PDMS@SiO2) films were prepared for that purpose: A hydrophilic film in which the thermal treatment causes an irreversible gradual increase of hydrophobicity; and a hydrophobic film that turns more hydrophilic upon thermal treatment. The opposite directionality of the change is dictated by the film substrate, on which the same hybrid is deposited. In both cases the thermal treatment induced a phase separation which caused the change in hydrophobicity. The magnitude of change in hydrophilicity/hydrophobicity is continuously controllable in both types of films by either the temperature or heating time. The films were characterized before and after heating by a variety of methods, including contact angle (CA) measurements with the sessile drop and the tilting plate methods, and by X-ray photoelectron spectroscopy (XPS) analysis. A thorough kinetic study was carried out, following the progress of the changes in the wettability property of the surfaces. The kinetics analyses proved that the changes in the wettability in all cases are due to phase separation processes, the directionality of which is determined by the treatment of the substrate on which the films are deposited. By monitoring the change of wettability (ΔCA) at various temperatures, an Arrhenius plot was obtained from which the activation energy and Arrhenius pre-exponential factor for the phase separation were derived, corroborating the proposed mechanism. To the best of our knowledge, this is the first use of phase separation behavior of a hybrid film in order to apply irreversible, thermally controllable change of surface wettability, tailored to proceed in opposite directions, and the first kinetic study of such a process.