Heat-Up Colloidal Synthesis of Shape-Controlled Cu-Se-S Nanostructures—Role of Precursor and Surfactant Reactivity and Performance in N2 Electroreduction

Copper selenide-sulfide nanostructures were synthesized using metal-organic chemical routes in the presence of Cu- and Se-precursors as well as S-containing compounds. Our goal was first to examine if the initial Cu/Se 1:1 molar proportion in the starting reagents would always lead to equiatomic composition in the final product, depending on other synthesis parameters which affect the reagents reactivity. Such reaction conditions were the types of precursors, surfactants and other reagents, as well as the synthesis temperature. The use of ‘hot-injection’ processes was avoided, focusing on ‘non-injection’ ones; that is, only heat-up protocols were employed, which have the advantage of simple operation and scalability. All reagents were mixed at room temperature followed by further heating to a selected high temperature. It was found that for samples with particles of bigger size and anisotropic shape the CuSe composition was favored, whereas particles with smaller size and spherical shape possessed a Cu2−xSe phase, especially when no sulfur was present. Apart from elemental Se, Al2Se3 was used as an efficient selenium source for the first time for the acquisition of copper selenide nanostructures. The use of dodecanethiol in the presence of trioctylphosphine and elemental Se promoted the incorporation of sulfur in the materials crystal lattice, leading to Cu-Se-S compositions. A variety of techniques were used to characterize the formed nanomaterials such as XRD, TEM, HRTEM, STEM-EDX, AFM and UV-Vis-NIR. Promising results, especially for thin anisotropic nanoplates for use as electrocatalysts in nitrogen reduction reaction (NRR), were obtained

Tailoring defects and nanocrystal transformation for optimal heating power in bimagnetic CoyFe1-yO@CoxFe3-xO4particles

The effects of cobalt incorporation in spherical heterostructured iron oxide nanocrystals (NCs) of sub-critical size have been explored by colloidal chemistry methods. Synchrotron X-ray total scattering methods suggest that cobalt (Co) substitution in rock salt iron oxide NCs tends to remedy their vacant iron sites, offering a higher degree of resistance to oxidative conversion. Self-passivation still creates a spinel-like shell, but with a higher volume fraction of the rock salt Co-containing phase in the core. The higher divalent metal stoichiometry in the rock salt phase, with increasing Co content, results in a population of unoccupied tetrahedral metal sites in the spinel part, likely through oxidative shell creation, involving an ordered defect-clustering mechanism, directly correlated to core stabilization. To shed light on the effects of Co-substitution and atomic-scale defects (vacant sites), Monte Carlo simulations suggest that the designed NCs, with desirable, enhanced magnetic properties (cf. exchange bias and coercivity), are developed with magnetocrystalline anisotropy which increases due to a relatively low content of Co ions in the lattice. The growth of optimally performing candidates combines also a strongly exchange-coupled system, secured through a high volumetric ratio rock salt phase, interfaced by a not so defective spinel shell. In view of these requirements, specific absorption rate (SAR) calculations demonstrate that the rock salt core sufficiently protected from oxidation and the heterostructure preserved over time, play a key role in magnetically mediated heating efficacies, for potential use of such NCs in magnetic hyperthermia applications. This journal i