In situ investigation of oxidation across a heterogeneous nanoparticle-support interface during metal support interactions.

Interactions between oxide supports and noble metal nanoparticles (NPs) is an area of intense research interest across all fields of catalysis. Oxygen spillover, metal support interactions (MSIs) and charge transfer are among many mechanisms observed and proposed as to how NP-support interfaces assist and enhance catalysis. This work studies the migration of oxygen across the Pd NP-CuO nanowire (NW) interface and beyond. X-ray photoelectron spectroscopy (XPS) and Kelvin probe force microscopy (KPFM) found an interaction between the Pd NP and CuO NW support, via the formation of PdO at the Pd-CuO interface. It was found, through in situ irradiation at high vacuum transmission electron microscopy (TEM), that oxygen enters the Pd NP lattice from the Pd-CuO interface via amorphization of the NP. Varying the amount of irradiation highlighted the different rates of amorphization of NPs, with full amorphization of a NP leading to the formation of an epitaxially driven PdO across the NPs. Interestingly, in situ heating in XPS observed a reduction to metallic Pd, found to be similarly amorphous during TEM investigation. On comparison with Pd supported on a non-reducible substrate - in which oxidation was found to proceed from the outer surface in, rather than the support interface (resulting in a PdO shell) - it is theorized that the oxidation and reduction of Pd on CuO forms a PdO NP surface full of Pd-PdO sites allowing for synergistic effects, of great use in the oxidation and hydrogenation of organic species.

Aggregation vs Surface Segregation: Antagonism over the Magnetic Behavior of NiCr Nanoparticles.

Annealing is a valuable method for fine-tuning the ultrasmall magnetic properties of alloy nanoparticles (NPs) by controlling their sizes, modifying their surfaces, and affecting their magnetic interactions. Herein, we study the effect of moderate annealing (450 °C) on strongly interacting NiCr nanoparticle assemblies (0 ≤ atom % Cr ≤ 15) immediately after deposition. Concurrent temperature-dependent electron microscopy and magnetization data demonstrate the interplay of two competing factors, namely, enhanced particle aggregation and element-specific surface segregation, on the magnetic properties, with the former boosting and the latter suppressing them. Strong interparticle interactions can lead to a magnetic response different from that of superparamagnetic particles, namely, from canonical spin-glass (0 atom % Cr) to correlated spin-glass (5-15 atom % Cr) behavior below higher spin-glass transition temperatures T g (20-350 K). The observation of "high-field susceptibility" below cryogenic temperatures (≤20 K) is ascribed to the presence of inhomogeneity/defects caused by Cr segregation. This work emphasizes the necessity of taking into account the delicate balance of such competing factors to understand the magnetic properties of nanoparticulate samples.

Nanoscale Heterogeneity of Multilayered Si Anodes with Embedded Nanoparticle Scaffolds for Li-Ion Batteries.

A new approach on the synthesis of Si anodes for Li-ion batteries is reported, combining advantages of both nanoparticulated and continuous Si films. A multilayered configuration prototype is proposed, comprising amorphous Si arranged in nanostructured, mechanically heterogeneous films, interspersed with Ta nanoparticle scaffolds. Particular structural features such as increased surface roughness, nanogranularity, and porosity are dictated by the nanoparticle scaffolds, boosting the lithiation process due to fast Li diffusion and low electrode polarization. Consequently, a remarkable charge/discharge speed is reached with the proposed anode, in the order of minutes (1200 mAh g-1 at 10 C). Moreover, nanomechanical heterogeneity self-limits the capacity at intermediate charge/discharge rates; as a consequence, exceptional cycleability is observed at 0.5 C, with 100% retention over 200 cycles with 700 mAh g-1. Higher capacity can be obtained when the first cycles are performed at 0.2 C, due to the formation of microislands, which facilitate the swelling of the active Si. This study indicates a method to tune the mechanical, morphological, and electrochemical properties of Si electrodes via engineering nanoparticle scaffolds, paving the way for a novel design of nanostructured Si electrodes for high-performance energy storage devices.

Control of Surface Segregation in Bimetallic NiCr Nanoalloys Immersed in Ag Matrix.

Cr-surface segregation is a main roadblock encumbering many magneto-biomedical applications of bimetallic M-Cr nanoalloys (where M = Fe, Co and Ni). To overcome this problem, we developed Ni95Cr5:Ag nanocomposite as a model system, consisting of non-interacting Ni95Cr5 nanoalloys (5 ± 1 nm) immersed in non-magnetic Ag matrix by controlled simultaneous co-sputtering of Ni95Cr5 and Ag. We employed Curie temperature (TC) as an indicator of phase purity check of these nanocomposites, which is estimated to be around the bulk Ni95Cr5 value of 320 K. This confirms prevention of Cr-segregation and also entails effective control of surface oxidation. Compared to Cr-segregated Ni95Cr5 nanoalloy films and nanoclusters, we did not observe any unwanted magnetic effects such as presence Cr-antiferromagnetic transition, large non-saturation, exchange bias behavior (if any) or uncompensated higher TC values. These nanocomposites films also lose their unique magnetic properties only at elevated temperatures beyond application requirements (≥800 K), either by showing Ni-type behavior or by a complete conversion into Ni/Cr-oxides in vacuum and air environment, respectively.

Engineering high-performance Pd core-MgO porous shell nanocatalysts via heterogeneous gas-phase synthesis.

We report on the design and synthesis of high performance catalytic nanoparticles with a robust geometry via magnetron-sputter inert-gas condensation. Sputtering of Pd and Mg from two independent neighbouring targets enabled heterogeneous condensation and growth of nanoparticles with controlled Pd core-MgO porous shell structure. The thickness of the shell and the number of cores within each nanoparticle could be tailored by adjusting the respective sputtering powers. The nanoparticles were directly deposited on glassy carbon electrodes, and their catalytic activity towards methanol oxidation was examined by cyclic voltammetry. The measurements indicated that the catalytic activity was superior to conventional bare Pd nanoparticles. As confirmed by electron microscopy imaging and supported by density-functional theory (DFT) calculations, we attribute the improved catalytic performance primarily to inhibition of Pd core sintering during the catalytic process by the metal-oxide shell.

Single CuO nanowires decorated with size-selected Pd nanoparticles for CO sensing in humid atmosphere.

We report on conductometric gas sensors based on single CuO nanowires and compare the carbon monoxide (CO) sensing properties of pristine as well as Pd nanoparticle decorated devices in humid atmosphere. Magnetron sputter inert gas aggregation combined with a quadrupole mass filter for cluster size selection was used for single-step Pd nanoparticle deposition in the soft landing regime. Uniformly dispersed, crystalline Pd nanoparticles with size-selected diameters around 5 nm were deposited on single CuO nanowire devices in a four point configuration. During gas sensing experiments in humid synthetic air, significantly enhanced CO response for CuO nanowires decorated with Pd nanoparticles was observed, which validates that magnetron sputter gas aggregation is very well suited for the realization of nanoparticle-functionalized sensors with improved performance.

Smart composite nanosheets with adaptive optical properties.

We report efficient design and facile synthesis of size-tunable organic/inorganic nanosheets, via a straightforward liquid exfoliation-adsorption process, of a near percolating gold (Au) thin film deposited onto a branched polyethylenimine (bPEI) matrix. The nanosheets are stiff enough to sustain their two-dimensional (2D) nature in acidic conditions, yet flexible enough to undergo a perfect reversible shape transformation to 1D nanoscrolls in alkaline conditions. The shape transformations, and associated optical property changes, at different protonation states are monitored by transmission electron microscopy (TEM), atomic force microscopy (AFM), UV-visible spectroscopy and zeta potential measurements. Because of their large surface area, both nanosheets and nanoscrolls could be used as capturing substrates for surface-enhanced Raman scattering (SERS) applications.

Coalescence-induced crystallisation wave in Pd nanoparticles.

Palladium nanoparticles offer an attractive alternative to bulk palladium for catalysis, hydrogen storage and gas sensing applications. Their performance depends strongly on surface structure; therefore, nanoparticle coalescence can play an important role, as it determines the resultant structure of the active sites where reactions (e.g. catalysis) actually take place, i.e. facets, edges, vertices or protrusions. With this in mind, we performed classical molecular dynamics (MD) simulations and magnetron-sputtering inert gas condensation depositions of palladium nanoparticles, supported by high-resolution transmission electron microscopy (HRTEM), to study the mechanisms that govern their coalescence. Surface energy minimisation drove the interactions initially, leading to the formation of an interface/neck, as expected. Intriguingly, at a later stage, atomic rearrangements triggered a crystallisation wave propagating through the amorphous nanoparticles, leading to mono- or polycrystalline fcc structures. In the case of crystalline nanoparticles, almost-epitaxial alignment occurred and the formation of twins and surface protrusions were observed.

Inoculation of silicon nanoparticles with silver atoms.

Silicon (Si) nanoparticles were coated inflight with silver (Ag) atoms using a novel method to prepare multicomponent heterostructured metal-semiconductor nanoparticles. Molecular dynamics (MD) computer simulations were employed, supported by high-resolution bright field (BF) transmission electron microscopy (HRTEM) and aberration-corrected scanning transmission electron microscopy (STEM) with a resolution ≤0.1 nm in high angle annular dark field (HAADF) mode. These studies revealed that the alloying behavior and phase dynamics during the coating process are more complex than when attaching hetero-atoms to preformed nanoparticles. According to the MD simulations, Ag atoms condense, nucleate and diffuse into the liquid Si nanoparticles in a process that we term "inoculation", and a phase transition begins. Subsequent solidification involves an intermediate alloying stage that enabled us to control the microstructure and crystallinity of the solidified hybrid heterostructured nanoparticles.