RESUMEN
In this work, we have developed a simple NiO-supported Pd nanocatalyst (Pd@NiO) for oxidant-free dehydrogenative oxidation of primary alcohols to carboxylic acids along with hydrogen gas as a byproduct. The catalyst has been characterized by techniques like XRD, HRTEM, SEM-EDX, XPS and ICP-AES. The nanostructured Pd@NiO material showed excellent dehydrogenative oxidation activity and outperformed the activity of free NiO or Pd nanoparticles supported on silica/carbon as a catalyst, which could be attributed to synergistic effect of Pd and NiO. A diverse range of aromatic and aliphatic primary alcohols could be efficiently converted to their corresponding carboxylates in high yields with a catalyst loading as low as 0.08 mol%. Notably, highly challenging biomass derived heterocyclic alcohols such as furfuryl alcohol and piperonyl alcohol can also be efficiently converted to their corresponding acids. Moreover, our catalyst can convert benzyl alcohol to benzoic acid on a gram scale with 89% yield. Interestingly, the H2 gas liberated in the reaction can also be used as a substrate for the hydrogenation of 3a to 4a in 65% yield. The nanostructured catalyst is highly reusable and no significant decrease in activity was observed after six reaction cycles. A kinetic study revealed that the reaction followed first-order kinetics with a rate constant of k = 1.47 × 10-4 s-1, under optimized conditions. The extent of reactivity of different functionalities towards dehydrogenation was also investigated using a Hammett plot showing good linearity.
RESUMEN
Fe3O4-SiO2 microspheres were synthesized by a three-step synthetic procedure involving silica coating, surface capping, and surface modification. These magnetic mesoporous microspheres were employed as sorbents for the incorporation of ultrasmall Ru nanoparticles (2-5 nm) followed by thermal aggregation of the microspheres for achieving better heterogeneity and low leaching. The Ru decorated Fe3O4-SiO2 microspheres (Ru@Fe3O4-CSM) were applied as chemoselective catalysts to convert more than 20 substituted nitroarenes to corresponding amines with good-to-excellent conversion (77-99%) and selectivity (70-100%) under mild conditions; the catalyst can be magnetically recovered within a frame of 90s (recovery time-lapse) and reused up to 5 times without significant decrease in activity or selectivity. Magnetic hysteresis studies were performed to elucidate the magnetic behavior of the ruthenium decorated materials.
RESUMEN
A facile ligand-assisted approach of synthesizing bimetallic Au-Pd nanoparticles supported on silica with a tunable core@shell structure is presented. Maneuvering the addition sequence of metal salts, both Aucore-Pdshell (Au@Pd-SiO2) and Pdcore-Aushell (Pd@Au-SiO2) nanoparticles were synthesized. The structures and compositions of the core-shell materials were confirmed by probe-corrected HRTEM, TEM-EDX mapping, EDS line scanning, XPS, PXRD, BET, FE-SEM-EDX and ICP analysis. The synergistic potentials of the core-shell materials were evaluated for two important reactions viz. hydrogenation of nitroarenes to anilines and hydration of nitriles to amides. In fact, in both the reactions, the Au-Pd materials exhibited superior performance over monometallic Au or Pd counterparts. Notably, among the two bimetallic materials, the one with Pdcore-Aushell structure displayed superior activity over the Aucore-Pdshell structure which could be attributed to the higher stability and uniform Au-Pd bimetallic interfaces in the former compared to the latter. Apart from enhanced synergism, high chemoselectivity in hydrogenation, wide functional group tolerance, high recyclability, etc. are other advantages of our system. A kinetic study has also been performed for the nitrile hydration reaction which demonstrates first order kinetics. Evaluation of rate constants along with a brief investigation on the Hammett parameters has also been presented.
