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Nanoscale heating by optical excitation of plasmonic nanoparticles offers a new perspective of controlling chemical reactions, where heat is not spatially uniform as in conventional macroscopic heating but strong temperature gradients exist around microscopic hot spots. In nanoplasmonics, metal particles act as a nanosource of light, heat, and energetic electrons driven by resonant excitation of their localized surface plasmon resonance. As an example of the coupling reaction of 4-nitrothiophenol into 4,4′-dimercaptoazobenzene, we show that besides the nanoscopic heat distribution at hot spots, the microscopic distribution of heat dictated by the spot size of the light focus also plays a crucial role in the design of plasmonic nanoreactors. Small sizes of laser spots enable high intensities to drive plasmon-assisted catalysis. This facilitates the observation of such reactions by surface-enhanced Raman scattering, but it challenges attempts to scale nanoplasmonic chemistry up to large areas, where the excess heat must be dissipated by one-dimensional heat transport.
Negatively charged flat gold nanotriangles, formed in a vesicular template phase and separated by an AOT-micelle-based depletion flocculation, were reloaded by adding a cationic polyelectrolyte, that is, a hyperbranched polyethylenimine (PEI). Heating the system to 100 degrees C in the presence of a gold chloride solution, the reduction process leads to the formation of gold nanoparticles inside the polymer shell surrounding the nanoplatelets. The gold nanoparticle formation is investigated by UV-vis spectroscopy, small-angle X-ray scattering, and dynamic light scattering measurements in combination with transmission electron microscopy. Spontaneously formed gold clusters in the hyperbranched PEI shell with an absorption maximum at 350 nm grow on the surface of the nanotriangles as hemispherical particles with diameters of similar to 6 nm. High-resolution micrographs show that the hemispherical gold particles are crystallized onto the {111} facets on the bottom and top of the platelet as well as on the edges without a grain boundary. Undulated gold nanoplatelet superstructures with special properties become available, which show a significantly modified performance in SERS-detected photocatalysis regarding both reactivity and enhancement factor.
Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl)sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 . 10(5) for the nanoflowers deposited on a silicon wafer.
The development of cheap and efficient electrocatalysts for the oxygen reduction reaction (ORR) is vital for the immediate commercialization of fuel cells which are still limited by the high cost and low performance of the utilized commercial Pt-based electrodes. As a promising alternative, this study reports on the synthesis of hierarchical iron-doped silver lotus flowers (AgFelotus) by a facile chemical procedure as robust and efficient ORR electrocatalysts. Succinic acid was used as a structure directing agent to tune the morphology of undoped and iron-doped silver particles. In the absence of succinic acid, ball-like silver particles were obtained, while using 2 mM succinic acid led to peony-like flower structures. The doping of silver peony-flowers with iron resulted in lotus-like flower structures with high electrocatalytic activity for ORR together with outstanding tolerance against poisoning with various hydrocarbon (HC) impurities, in situ generated during fuel cell operation, as well as different fuels from anodic crossover. AgFelotus exhibited a superior ORR activity with more than 40 times higher stability than the commercial Pt/C catalyst in alkaline media. This substantial performance enhancement is attributed to the unique lotus-like flower structures providing more electroactive surface sites, in addition to the iron dopants which facilitate ORR charge transfer.