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  1. Abstract

    Plasmonic nanoparticles that can be manipulated with magnetic fields are of interest for advanced optical applications, diagnostics, imaging, and therapy. Alignment of gold nanorods yields strong polarization‐dependent extinction, and use of magnetic fields is appealing because they act through space and can be quickly switched. In this work, cationic polyethyleneimine‐functionalized superparamagnetic Fe3O4nanoparticles (NPs) are deposited on the surface of anionic gold nanorods coated with bovine serum albumin. The magnetic gold nanorods (MagGNRs) obtained through mixing maintain the distinct optical properties of plasmonic gold nanorods that are minimally perturbed by the magnetic overcoating. Magnetic alignment of the MagGNRs arising from magnetic dipolar interactions on the anisotropic gold nanorod core is comprehensively characterized, including structural characterization and enhancement (suppression) of the longitudinal surface plasmon resonance and suppression (enhancement) of the transverse surface plasmon resonance for light polarized parallel (orthogonal) to the magnetic field. The MagGNRs can also be driven in rotating magnetic fields to rotate at frequencies of at least 17 Hz. For suitably large gold nanorods (148 nm long) and Fe3O4NPs (13.4 nm diameter), significant alignment is possible even in modest (<500 Oe) magnetic fields. An analytical model provides a unified understanding of the magnetic alignment of MagGNRs.

     
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  2. Abstract

    Transition metal chalcogenide nanoparticles (NPs) are of interest for energy applications, including batteries, supercapacitors, and electrocatalysis. Many methods have been established for synthesizing Ni NPs, and conversion chemistry to form Ni oxide and phosphides from template Ni NPs is well‐understood. Sulfidation and selenidation of Ni NPs have been much less explored, however. We report a method for the conversion of Ni template NPs into sulfide and selenide product NPs using elemental sulfur, 1‐hexadecanthiol, thiourea, trioctylphosphine sulfide, elemental selenium, and selenourea. While maintaining mole ratios of 2 mmol sulfur/selenium precursor: mmol Ni, products with phases of Ni3S2, Ni9S8, NiS, NiSO4·6H2O, Ni3S4, Ni3Se2, and NiSe have been obtained. The products have voids that form through the Kirkendall effect during interdiffusion. Trends relating the chemical properties of the precursors to the phases of the products have been identified. While some precursors contained phosphorus, there was no significant incorporation of phosphorus in any of the products. An increase of the NP size during sulfidation and selenidation is consistent with ripening. The application of Ni sulfide and selenide NPs as electrocatalysts for the hydrogen evolution reaction is also demonstrated.

     
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