Core-shell nanocomposites (R-Au) bearing well-defined gold nanoparticles as surface atoms of variable sizes (8-55 nm) have been synthesized exploiting polystyrene-based commercial anion exchangers. Immobilization of gold nanoparticles, prepared by the Frens method, onto the resin beads in the chloride form is possible by the ready exchange of the citrate-capped negatively charged gold particles. The difficulty of nanoparticle loading, avoiding aggregation, has been solved by stepwise operation. Analysis of the gold particles after immobilization and successive elution confirm the unaltered particle morphology while compared to those of the citrate-capped gold particles in colloidal dispersion. It was observed that the rate of the reaction increases with the increase in catalyst loading, which suggests the catalytic behavior of the gold nanoparticles for the reduction of the aromatic nitrocompounds. The rate constant, k, was found to be proportional to the total surface area of the nanoparticles in the system. Kinetic study for the reduction of a series of aromatic nitrocompounds reveals that the aromatic nitrocompound exclusively adsorbs to atop sites of gold particles and that the rate of the reduction reaction increases as the particle size decreases. Similar reaction kinetics was observed involving gold sol of variable size (homogeneous catalysis) as catalyst. The induction time and the activation energy of the reaction decreases with decrease in particle size indicating the decrease in activation energy for the smaller particles, which also speaks for the increase of surface roughness with decrease in particle size. The observed rate dependence, in relation to particle size, is attributed to a higher reactivity of the coordinatively unsaturated surface atoms in small particles compared to low-index surface atoms prevalent in larger particles.
Beta-cyclodextrin (β-CD) in alkaline solution has been observed to produce mono-and bimetallic nanoparticles of silver and gold and to provide in-house stability to both types of particles. Thus, the weak reducing capability of the β-CD molecule (oxidation occurs at +1.33 V vs Ag/AgCl) and its unique kinetic control over the evolution of both normal and inverted core-shell bimetallic architectures have been established. The structure and composition of the bimetallic particles were characterized by UV-visible spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, electron dispersive spectroscopy, and X-ray photoelectron spectroscopy. Bimetallic core-shell particles containing silver shells have been shown to provide an elegant SERS-active substrate compared to the corresponding monometallic nanoparticles, and therefore, they highlight the importance of electronic ligand effects on the enhancement of the Raman signals of molecular probes on nanostructured metallic surfaces.
The immobilization of gold nanoparticles in anion exchange resin and their quantitative retrieval by means of a cationic surfactant, cetylpyridinium chloride, is studied. The resin-bound gold nanoparticles (R-Au) have been used successfully as a solid-phase catalyst for the reduction of 4-nitrophenol by sodium borohydride. At the end of the reaction, the solid matrix remains activated and separated from the product. The recycling of catalyst particles after the quantitative reduction of 4-nitrophenol and the recovery of gold nanoparticles with unaffected particle morphology from the resin-bound gold nanoparticle entity have been reported.
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