Bimetallic plasmonic nanoparticles enable tuning of the optical response and chemical stability by variation of the composition. The present numerical simulation study compares Ag-Au alloy, Ag@Au core-shell, and Au@Ag core-shell bimetallic plasmonic nanoparticles of both spherical and anisotropic (nanotriangle and nanorods) shapes. By studying both spherical and anisotropic (with LSPR in the near-infrared region) shapes, cases with and without interband transitions of Au can be decoupled. Explicit comparisons are facilitated by numerical models supported by careful validation and examination of optical constants of Au-Ag alloys reported in literature. Although both Au-Ag core-shell and alloy nanoparticles exhibit an intermediary optical response between that of pure Ag and Au nanoparticles, there are noticeable differences in the spectral characteristics. Also, the effect of the bimetallic constitution in anisotropic nanoparticles is starkly different from that in spherical nanoparticles due to the absence of Au interband transitions in the former case. In general, the improved chemical stability of Ag nanoparticles by incorporation of Au comes with a cost of reduction in plasmonic enhancement, also applicable to anisotropic nanoparticles with a weaker effect. A photothermal heat transfer study confirms that increased absorption by the incorporation of Au in spherical Ag nanoparticles also results in an increased steady state temperature. On the other hand, anisotropic nanoparticles are inherently better absorbers, hence better photothermal sources and their photothermal properties are apparently not strongly affected by the incorporation of one metal in the other. This study of the optical/spectral and photothermal characteristics of bimetallic Au-Ag alloy versus core-shell nanoparticles provides a detailed physical insight for the development of new taylor-made plasmonic nanostructures.
Assemblies of closely separated gold nanoparticles exhibit a strong collective plasmonic response due to coupling of the plasmon modes of the individual nanostructures. In the context of self-assembly of nanoparticles, closed packed 2D clusters of spherical nanoparticles present an important composite system that promises numerous applications. The present study probes the collective plasmonic characteristics and resulting photothermal behavior of closed packed 2D Au nanoparticle clusters in order to delineate the effects of cluster size, inter-particle distance and particle size. Smaller nanoparticles (20 nm and 40 nm in diameter) that exhibit low individual scattering and high absorption were considered for their relevance to photothermal applications. In contrast to typical literature studies, the present study compares the optical response of clusters of different sizes ranging from a single nanoparticle up to large assemblies of 61 nanoparticles. Increasing the cluster size induces significant changes to the spectral position and optophysical characteristics. Based on the model outcome, an optimal cluster size for maximum absorption per nanoparticle is also determined for enhanced photothermal effects. The effect of particle size and interparticle distance is investigated in order to elucidate the nature of interaction in terms of near-field and farfield coupling. The photothermal effect resulting from absorption is compared for different cluster sizes and inter-particle distances considering a homogeneous water medium. A strong dependence of the steady state temperature of the nanoparticles on the cluster size, particle position in the cluster, incident light polarization and inter-particle distance provides new physical insight in local temperature control of plasmonic nanostructures.
Development of a high surface area and efficient visible light induced photocatalyst on a large scale is a promising task from the practical perspective. In this study, visible light active C-doped anatase TiO multi-tubes were synthesized using banana (Musa acuminata) stem fiber as a sacrificial template, removed by calcination at 450 °C. During the calcination process, the lattice of anatase TiO phase was doped with C, and obtained multi-tubes showed high surface area (∼99 m/g) with a mesoporous structure made of ∼15 ± 3 nm nanoparticles. The synthesized TiO multi-tubes showed an enhanced light absorption property in the whole visible light region and good thermal stability of the anatase phase up to 750 °C. The synthesized C-doped TiO multi-tubes manifest an excellent photocatalytic activity for the reduction of Cr (VI) to Cr(III) under the visible light exposure. This process may have lots of practical importance as the method of synthesis of the catalyst is novel and the multi-tubes structure can be synthesized on a large scale through a quick and economical way with excellent photocatalytic activity. This novel multi-tubes structure may also be useful for photovoltaics, antimicrobial, and Li-batteries applications in the future.
The functionalization of photocatalytic metal oxide nanoparticles of TiO 2 , ZnO, WO 3 and CuO with amineterminated (oleylamine) and thiol-terminated (dodecane-1thiol) alkyl-chain ligands was studied under ambient conditions. A high selectivity was observed in the binding specificity of a ligand towards nanoparticles of these different oxides. It was observed that oleylamine binds stably to only TiO 2 and WO 3 , whereas dodecane-1-thiol binds stably only to ZnO and CuO. Similarly, polar-to-nonpolar solvent phase transfer of TiO 2 and WO 3 nanoparticles could be achieved by using oleylamine, but not dodecane-1-thiol, whereas the opposite holds for ZnO and CuO. The surface chemistry of ligand-functionalized nanoparticles was probed by attenu-ated total reflectance (ATR)-FTIR spectroscopy, which enabled the occupation of the ligands at the active sites to be elucidated. The photostability of the ligands on the nanoparticle surface was determined by the photocatalytic selfcleaning properties of the material. Although TiO 2 and WO 3 degrade the ligands within 24 h under both UV and visible light, ligands on ZnO and CuO remain unaffected. The gathered insights are also highly relevant from an application point of view. As an example, because the ligand-functionalized nanoparticles are hydrophobic in nature, they can be self-assembled at the air-water interface to give nanoparticle films with demonstrated photocatalytic as well as antifogging properties.
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