The electronic structure, surface properties, and in situ N2O decomposition of mechanochemically synthesised LaMnO3.

The use of mechanochemistry to prepare catalytic materials is of significant interest; it offers an environmentally beneficial, solvent-free, route and produces highly complex structures of mixed amorphous and crystalline phases. This study reports on the effect of milling atmosphere, either air or argon, on mechanochemically prepared LaMnO3 and the catalytic performance towards N2O decomposition (deN2O). In this work, high energy resolution fluorescence detection (HERFD), X-ray absorption near edge structure (XANES), X-ray emission, and X-ray photoelectron spectroscopy (XPS) have been used to probe the electronic structural properties of the mechanochemically prepared materials. Moreover, in situ studies using near ambient pressure (NAP)-XPS, to follow the materials during catalysis, and high pressure energy dispersive EXAFS studies, to mimic the preparation conditions, have also been performed. The studies show that there are clear differences between the air and argon milled samples, with the most pronounced changes observed using NAP-XPS. The XPS results find increased levels of active adsorbed oxygen species, linked to the presence of surface oxide vacancies, for the sample prepared in argon. Furthermore, the argon milled LaMnO3 shows improved catalytic activity towards deN2O at lower temperatures compared to the air milled and sol-gel synthesised LaMnO3. Assessing this improved catalytic behaviour during deN2O of argon milled LaMnO3 by in situ NAP-XPS suggests increased interaction of N2O at room temperature within the O 1s region. This study further demonstrates the complexity of mechanochemically prepared materials and through careful choice of characterisation methods how their properties can be understood.

Atomic resolution monitoring of cation exchange in CdSe-PbSe heteronanocrystals during epitaxial solid-solid-vapor growth.

Here, we show a novel solid-solid-vapor (SSV) growth mechanism whereby epitaxial growth of heterogeneous semiconductor nanowires takes place by evaporation-induced cation exchange. During heating of PbSe-CdSe nanodumbbells inside a transmission electron microscope (TEM), we observed that PbSe nanocrystals grew epitaxially at the expense of CdSe nanodomains driven by evaporation of Cd. Analysis of atomic-resolution TEM observations and detailed atomistic simulations reveals that the growth process is mediated by vacancies.

Low-dimensional semiconductor superlattices formed by geometric control over nanocrystal attachment.

Oriented attachment, the process in which nanometer-sized crystals fuse by atomic bonding of specific crystal facets, is expected to be more difficult to control than nanocrystal self-assembly that is driven by entropic factors or weak van der Waals attractions. Here, we present a study of oriented attachment of PbSe nanocrystals that counteract this tuition. The reaction was studied in a thin film of the suspension casted on an immiscible liquid at a given temperature. We report that attachment can be controlled such that it occurs with one type of facets exclusively. By control of the temperature and particle concentration we obtain one- or two-dimensional PbSe single crystals, the latter with a honeycomb or square superimposed periodicity in the nanometer range. We demonstrate the ability to convert these PbSe superstructures into other semiconductor compounds with the preservation of crystallinity and geometry.

Fluidized Bed Chemical Vapor Deposition on Hard Carbon Powders to Produce Composite Energy Materials.

Herein, we report a general route for the uniform coating of hard carbon (HC) powders via fluidized bed chemical vapor deposition. Carbon-based fine powders are excellent substrate materials for many catalytic and electrochemical applications but intrinsically difficult to fluidize and prone to elutriation. The reactor was designed to achieve as much retention of powders as possible, supported by a computational fluid dynamics study to assess the hydrodynamic behavior for varying gaseous flow rates. Solutions of the tin seleno- and thio-ether complexes [SnCl4{nBuSe(CH2)3SenBu}] and [SnCl4{nBuS(CH2)3SnBu}] were used as single source precursors and injected at high temperature into a fluidized bed of HC powders under nitrogen flow. The method allowed for the synthesis of HC-SnSx-SnSe2 composites at the gram scale with potential applications in electrocatalysis and sodium-ion battery anodes.

Structural investigations into colour-tuneable fluorescent InZnP-based quantum dots from zinc carboxylate and aminophosphine precursors.

Fluorescent InP-based quantum dots have emerged as valuable nanomaterials for display technologies, biological imaging, and optoelectronic applications. The inclusion of zinc can enhance both their emissive and structural properties and reduce interfacial defects with ZnS or CdS shells. However, the sub-particle distribution of zinc and the role this element plays often remains unclear, and it has previously proved challenging to synthesise Zn-alloyed InP-based nanoparticles using aminophosphine precursors. In this report, we describe the synthesis of alloyed InZnP using zinc carboxylates, achieving colour-tuneable fluorescence from the unshelled core materials, followed by a one-pot ZnS or CdS deposition using diethyldithiocarbamate precursors. Structural analysis revealed that the "core/shell" particles synthesised here were more accurately described as homogeneous extended alloys with the constituent shell elements diffusing through the entire core, including full-depth inclusion of zinc.

Three-dimensional atomic imaging of colloidal core-shell nanocrystals.

Colloidal core-shell semiconductor nanocrystals form an important class of optoelectronic materials, in which the exciton wave functions can be tailored by the atomic configuration of the core, the interfacial layers, and the shell. Here, we provide a trustful 3D characterization at the atomic scale of a free-standing PbSe(core)-CdSe(shell) nanocrystal by combining electron microscopy and discrete tomography. Our results yield unique insights for understanding the process of cation exchange, which is widely employed in the synthesis of core-shell nanocrystals. The study that we present is generally applicable to the broad range of colloidal heteronanocrystals that currently emerge as a new class of materials with technological importance.

Enthalpy and entropy of nanoparticle association from temperature-dependent cryo-TEM.

Quantum dots form equilibrium structures in liquid dispersions, due to thermodynamic forces that are often hard to quantify. Analysis of these structures, visualized using cryogenic electron microscopy, yields their formation free energy. Here we show that the nanoparticle interaction free energy can be further separated into the enthalpic and entropic contributions, using the temperature dependence of the assembled structures. Monodisperse oleic acid-capped PbSe nanoparticles dispersed in decalin were used as a model system, and the temperature-dependent equilibrium structures were imaged by cryo-TEM, after quenching from different initial temperatures. The interaction enthalpy and entropy follow from van 't Hoff's exact equation for the temperature dependence of thermodynamic equilibria, now applied to associating nanoparticles. The enthalpic component gives the magnitude of the contact interaction, which is crucial information in understanding the energetics of the self-assembly of nanoparticles into ordered structures.

Anisotropic Plasmonic CuS Nanocrystals as a Natural Electronic Material with Hyperbolic Optical Dispersion.

Copper sulfide nanocrystals have recently been studied due to their metal-like behavior and strong plasmonic response, which make them an attractive material for nanophotonic applications in the near-infrared spectral range; however, the nature of the plasmonic response remains unclear. We have performed a combined experimental and theoretical study of the optical properties of copper sulfide colloidal nanocrystals and show that bulk CuS resembles a heavily doped p-type semiconductor with a very anisotropic energy band structure. As a consequence, CuS nanoparticles possess key properties of relevance to nanophotonics applications: they exhibit anisotropic plasmonic behavior in the infrared and support optical modes with hyperbolic dispersion in the 670-1050 nm spectral range. We also predict that the ohmic loss is low compared to conventional plasmonic materials such as noble metals in the NIR. The plasmonic resonances can be tuned by controlling the size and shape of the nanocrystals, providing a playground for future nanophotonic applications in the near-infrared.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion.

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer-Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters.

Exchange-coupled bimagnetic cobalt/iron oxide branched nanocrystal heterostructures.

A colloidal seeded-growth strategy, relying on time-programmed delivery of selected stabilizing surfactants, has been developed to synthesize bimagnetic hybrid nanocrystals (HNCs) that consist of a single-crystal tetrapod-shaped skeleton of ferrimagnetic (FiM) iron oxide functionalized with multiple polycrystalline spherical domains of ferromagnetic (FM) Co. Due to the direct bonding interfaces formed between the two materials at the relevant junction regions, the HNCs exhibit FiM-FM exchange coupling, which transcribes into a rich scenario of significantly modified properties (not otherwise achievable with any of the single components or with their physical mixtures), including higher saturation magnetization and coercitivity values, exchange biasing, and enhanced thermal stability due to induced extra anisotropy. The availability of these new types of HNCs suggests that development of appropriate synthetic tools for arranging distinct material domains in predetermined spatial arrangements could lead to a more rational design of nanoheterostructures potentially exploitable as active elements in future generations of magnetic recording devices.

Advances in the chemical fabrication of complex multimaterial nanocrystals.

In this work, recent achievements of nanochemistry research in the fabrication of colloidal nanoheterostructures are reviewed through revisiting relevant papers and related patents. Attention is focused on newly conceived generations of hybrid nanocrystals (HNCs) with a topologically controlled composition, in which size and shape tailored domains of different inorganic materials are permanently assembled together in a single multifunctional particle. Strategies for accessing HNCs in various configurations, such as core/shell systems, hetero-oligomers based on nearly spherical portions, and highly asymmetric nanostructures comprising joint sections with different shapes, are discussed. The chemical-physical properties and technological advantages offered by such complex nanocrystals are also highlighted.

Topologically controlled growth of magnetic-metal-functionalized semiconductor oxide nanorods.

Colloidal semiconductor-magnetic hybrid nanocrystals with topologically controlled composition are fabricated by heterogeneous nucleation of spherical epsilon-Co domains onto anatase TiO2 nanorods. The latter can be selectively decorated at either their tips or at multiple locations along their longitudinal sidewalls, forming lattice-matched heterointerfaces regardless of the metal deposition sites. The possibility of switching between either heterostructure growth modes arises from the facet-dependent chemical reactivity of the oxide seeds, which is governed mainly by selective adhesion of the surfactants rather than by small differences in misfit-induced interfacial strain at the relevant junction points.