Bulk iron pyrite as a catalyst for the selective hydrogenation of nitroarenes.

Bulk iron pyrite (FeS2) functions as an inexpensive, Earth-abundant, off-the-shelf catalyst capable of selectively hydrogenating a broad scope of substituted nitroarenes to their corresponding aniline derivatives using molecular hydrogen.

Semi-preparative asymmetrical flow field-flow fractionation: A closer look at channel dimensions and separation performance.

The design and performance of a semi-preparative asymmetrical flow field-flow fractionation (SP-AF4) channel are investigated with the objective of better understanding and exploiting the relationship between channel dimensions, sample loading, and resolution. Most size-based separations of nanometer and submicrometer particles are currently limited to analytical scale quantities (<100µg). However, there is a strong need to fractionate and collect larger quantities so that fundamental properties of the more narrowly dispersed fractions can be studied using additional characterization methods and for subsequent applications. In this work, dimensions of the spacer that defines the form of SP-AF4 channels are varied and their performances are assessed with respect to sample focusing position and loading. Separations are performed in aqueous and organic carrier fluids. A critical evaluation of channel dimensions showed that increasing the channel breadth is a practical and effective route to maintaining separation resolution while increasing sample loads to milligram quantities. Good size resolution (∼1.0) is achieved for separations of 10mg of 50 and 100nm silica nanoparticles suspended in water and up to 0.6mg of ∼10 to 35nm inorganic hybrid nanoparticles suspended in tetrahydrofuran. This work represents important advances in the understanding of SP-AF4 separations and extends sample loading capacities in both aqueous and organic solvents.

Microscopic Investigation of Chemoselectivity in Ag-Pt-Fe3O4 Heterotrimer Formation: Mechanistic Insights and Implications for Controlling High-Order Hybrid Nanoparticle Morphology.

Three-component hybrid nanoparticle heterotrimers, which are important multifunctional constructs that underpin diverse applications, are commonly synthesized by growing a third domain off of a two-component heterodimer seed. However, because heterodimer seeds expose two distinct surfaces that often can both support nucleation and growth, selectively targeting one particular surface is critical for exclusively accessing a desired configuration. Understanding and controlling nucleation and growth therefore enables the rational formation of high-order hybrid nanoparticles. Here, we report an in-depth microscopic investigation that probes the chemoselective addition of Ag to Pt-Fe3O4 heterodimer seeds to form Ag-Pt-Fe3O4 heterotrimers. We find that the formation of the Ag-Pt-Fe3O4 heterotrimers initiates with indiscriminate Ag nucleation onto both the Pt and Fe3O4 surfaces of Pt-Fe3O4, followed by surface diffusion and coalescence of Ag onto the Pt surface to form the Ag-Pt-Fe3O4 product. Control experiments reveal that the size of the Ag domain of Ag-Pt-Fe3O4 correlates with the overall surface area of the Pt-Fe3O4 seeds, which is consistent with the coalescence of Ag through a surface-mediated process and can also be exploited to tune the size of the Ag domain. Additionally, we observe that small iron oxide islands on the Pt surface of the Pt-Fe3O4 seeds, deposited during the formation of Pt-Fe3O4, define the morphology of the Ag domain, which in turn influences its optical properties. These results provide unprecedented microscopic insights into the pathway by which Ag-Pt-Fe3O4 heterotrimer nanoparticles form and uncover new design guidelines for the synthesis of high-order hybrid nanoparticles with precisely targeted morphologies and properties.