Defect-assisted electronic metal-support interactions: tuning the interplay between Ru nanoparticles and CuO supports for pH-neutral oxygen evolution.

Electronic metal-support interactions (EMSIs) comprise an area of intense study, the manipulation of which is of paramount importance in the improvement of heterogeneous metal nanoparticle (NP) supported catalysts. EMSI is the transfer of charge from the support to NP, enabling more effective adsorption and interaction of reactants during catalysis. Ru NPs on CuO supports show different levels of EMSI (via charge transfer) depending on their crystal structure, with multiple twinned NPs showing greater potential for EMSI. We use magnetron-assisted gas phase aggregation for the synthesis of batches of Ru NPs with different populations of single crystal and multiple twinned nanoparticles, which were deposited on CuO nanowires (NWs). The surface charging of the Ru-CuO catalysts was investigated by Kelvin probe force microscopy (KPFM) and X-ray photoelectron spectroscopy (XPS). By doubling the population of multiple twinned NPs, the surface potential of the Ru-CuO catalysts increases roughly 4 times, coinciding with a similar increase in the amount of Ru4+. Therefore, tuning the amount of EMSI in a catalyst is possible through changing the population of multiple twinned Ru NPs in the catalyst. Increasing the amount of multiple twin NPs resulted in improved activity in the oxygen evolution reaction (a roughly 2.5 times decrease in the overpotentials when the population of multiple twinned NPs is increased) and better catalyst stability. This improvement is attributed to the fact that the multiple twin NPs maintained a metallic character under oxidation conditions (unlike single crystal NPs) due to the EMSI between the NP and support.

Non-enzymatic and highly sensitive lactose detection utilizing graphene field-effect transistors.

Field-effect transistor (FET) biosensors based on low-dimensional materials are capable of highly sensitive and specific label-free detection of various analytes. In this work, a FET biosensor based on graphene decorated with gold nanoparticles (Au NPs) was fabricated for lactose detection in a liquid-gate measurement configuration. This graphene device is functionalized with a carbohydrate recognition domain (CRD) of the human galectin-3 (hGal-3) protein to detect the presence of lactose from the donor effect of lectin - glycan affinity binding on the graphene. Although the detection of lactose is important because of its ubiquitous presence in food and for disease related applications (lactose intolerance condition), in this work we exploit the lectin/carbohydrate interaction to develop a device that in principle could specifically detect very low concentrations of any carbohydrate. The biosensor achieved an effective response to lactose concentrations over a dynamic range from 1 fM to 1 pM (10-15 to 10-12 mol L-1) with a detection limit of 200 aM, a significant enhancement over previous electrochemical graphene devices. The FET sensor response is also specific to lactose at aM concentrations, indicating the potential of a combined lectin and graphene FET (G-FET) sensor to detect carbohydrates at high sensitivity and specificity for disease diagnosis.

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.

In Situ Observation of Metal to Metal Oxide Progression: A Study of Charge Transfer Phenomenon at Ru-CuO Interfaces.

Surface charge and charge transfer between nanoclusters and oxide supports are of paramount importance to catalysis, surface plasmonics, and optical energy harvesting areas. At present, high-energy X-rays and theoretical investigation are always required to determine the chemical state changes in the nanoclusters and the oxide supports, as well as the underlying transfer charge between them. This work presents the idea of using chrono-conductometric measurements to determine the chemical states of the Ru nanoclusters on CuO supports. Both icosahedral and single-crystal hexagonal close-packed Ru nanoclusters were deposited through gas-phase synthesis. To study the charge transfer phenomenon at the interface, a bias was applied to cupric oxide nanowires with metallic nanocluster decoration. In situ conductometric measurements were performed to observe the evolution of Ru into RuOx under heating conditions. Structural elucidation techniques such as transmission electron microscopy, X-ray photoelectron spectroscopy, and Kelvin probe force microscopy were employed to study the corresponding progression of structure, chemical ordering, and surface potential, respectively, as Ru(0) was oxidized to RuOx on the supporting oxide surface. Experimental and theoretical investigation of charge transfer between the nanocluster and oxide support highlighted the importance of metallic character and structure of the nanoclusters on the interfacial charge transfer, thus allowing the investigation of surface charge behavior on oxide-supported catalysts, in situ, during catalytic operation via conductometric measurements.

Site-Specific Wetting of Iron Nanocubes by Gold Atoms in Gas-Phase Synthesis.

A key challenge in nanotechnology is the rational design of multicomponent materials that beat the properties of their elemental counterparts. At the same time, when considering the material composition of such hybrid nanostructures and the fabrication process to obtain them, one should favor the use of nontoxic, abundant elements in view of the limited availability of critical metals and sustainability. Cluster beam deposition offers a solvent- and, therefore, effluent-free physical synthesis method to achieve nanomaterials with tailored characteristics. However, the simultaneous control of size, shape, and elemental distribution within a single nanoparticle in a small-size regime (sub-10 nm) is still a major challenge, equally limiting physical and chemical approaches. Here, a single-step nanoparticle fabrication method based on magnetron-sputtering inert-gas condensation is reported, which relies on selective wetting of specific surface sites on precondensed iron nanocubes by gold atoms. Using a newly developed Fe-Au interatomic potential, the growth mechanism is decomposed into a multistage model implemented in a molecular dynamics simulation framework. The importance of growth kinetics is emphasized through differences between structures obtained either experimentally or computationally, and thermodynamically favorable configurations determined via global optimization techniques. These results provide a roadmap for engineering complex nanoalloys toward targeted applications.

Nanoassemblies of ultrasmall clusters with remarkable activity in carbon dioxide conversion into C1 fuels.

Cu nanoassemblies formed transiently during reaction from size-selected subnanometer Cu4 clusters supported on amorphous OH-terminated alumina convert CO2 into methanol and hydrocarbons under near-atmospheric pressure at rates considerably higher than those of individually standing Cu4 clusters. An in situ characterization reveals that the clusters self-assemble into 2D nanoassemblies at higher temperatures which then disintegrate upon cooling down to room temperature. DFT calculations postulate a formation mechanism of these nanoassemblies by hydrogen-bond bridges between the clusters and H2O molecules, which keep the building blocks together while preventing their coalescence.

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.

In situ chemoresistive sensing in the environmental TEM: probing functional devices and their nanoscale morphology.

In situ transmission electron microscopy provides exciting opportunities to address fundamental questions and technological aspects related to functional nanomaterials, including the structure-property relationships of miniaturized electronic devices. Herein, we report the in situ chemoresistive sensing in the environmental transmission electron microscope (TEM) with a single SnO2 nanowire device, studying the impact of surface functionalization with heterogeneous nanocatalysts. By detecting toxic carbon monoxide (CO) gas at ppm-level concentrations inside the microscope column, the sensing properties of a single SnO2 nanowire were characterized before and after decoration with hybrid Fe-Pd nanocubes. The structural changes of the supported nanoparticles induced by sensor operation were revealed, enabling direct correlation with CO sensing properties. Our novel approach is applicable for a broad range of functional nanomaterials and paves the way for future studies on the relationship between chemoresistive properties and nanoscale morphology.

Kinetic trapping through coalescence and the formation of patterned Ag-Cu nanoparticles.

In recent years, due to its inherent flexibility, magnetron-sputtering has been widely used to synthesise bi-metallic nanoparticles (NPs) via subsequent inert-gas cooling and gas-phase condensation of the sputtered atomic vapour. Utilising two separate sputter targets allows for good control over composition. Simultaneously, it involves fast kinetics and non-equilibrium processes, which can trap the nascent NPs into metastable configurations. In this study, we observed such configurations in immiscible, bi-metallic Ag-Cu NPs by scanning transmission electron microscopy (S/TEM) and electron energy-loss spectroscopy (EELS), and noticed a marked difference in the shape of NPs belonging to Ag- and Cu-rich samples. We explained the formation of Janus or Ag@Cu core/shell metastable structures on the grounds of in-flight mixed NP coalescence. We utilised molecular dynamics (MD) and Monte Carlo (MC) computer simulations to demonstrate that such configurations cannot occur as a result of nanoalloy segregation. Instead, sintering at relatively low temperatures can give rise to metastable structures, which eventually can be stabilised by subsequent quenching. Furthermore, we compared the heteroepitaxial diffusivities along various surfaces of both Ag and Cu NPs, and emphasised the differences between the sintering mechanisms of Ag- and Cu-rich NP compositions: small Cu NPs deform as coherent objects on large Ag NPs, whereas small Ag NPs dissolve into large Cu NPs, with their atoms diffusing along specific directions. Taking advantage of this observation, we propose controlled NP coalescence as a method to engineer mixed NPs of a unique, patterned core@partial-shell structure, which we refer to as a "glass-float" (ukidama) structure.

Formation Mechanism of Fe Nanocubes by Magnetron Sputtering Inert Gas Condensation.

In this work, we study the formation mechanisms of iron nanoparticles (Fe NPs) grown by magnetron sputtering inert gas condensation and emphasize the decisive kinetics effects that give rise specifically to cubic morphologies. Our experimental results, as well as computer simulations carried out by two different methods, indicate that the cubic shape of Fe NPs is explained by basic differences in the kinetic growth modes of {100} and {110} surfaces rather than surface formation energetics. Both our experimental and theoretical investigations show that the final shape is defined by the combination of the condensation temperature and the rate of atomic deposition onto the growing nanocluster. We, thus, construct a comprehensive deposition rate-temperature diagram of Fe NP shapes and develop an analytical model that predicts the temporal evolution of these properties. Combining the shape diagram and the analytical model, morphological control of Fe NPs during formation is feasible; as such, our method proposes a roadmap for experimentalists to engineer NPs of desired shapes for targeted applications.

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.

A facile single-step synthesis of ternary multicore magneto-plasmonic nanoparticles.

We report a facile single-step synthesis of ternary hybrid nanoparticles (NPs) composed of multiple dumbbell-like iron-silver (FeAg) cores encapsulated by a silicon (Si) shell using a versatile co-sputter gas-condensation technique. In comparison to previously reported binary magneto-plasmonic NPs, the advantage conferred by a Si shell is to bind the multiple magneto-plasmonic (FeAg) cores together and prevent them from aggregation at the same time. Further, we demonstrate that the size of the NPs and number of cores in each NP can be modulated over a wide range by tuning the experimental parameters.

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.

Multifunctional nanovehicles for combined 5-fluorouracil and gold nanoparticles based on the nanoprecipitation method.

To facilitate the administration of combined 5-Fluorouracil (5-FU) and gold nanoparticles (for photothermal treatment purposes), we developed 5-FU-gold-poly(lactide-co-glycolic acid) (5-FU-Au-PLGA) nanovehicles, via the nanoprecipitation method. The gold nanoparticles were incorporated inside the 5-FU-PLGA carriers using a roller mixer. Morphological analysis using atomic force microscopy (AFM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), indicated uniform, singly separated spherical nanoparticles (NPs). Drug content, recovery and entrapment in the NPs were approximated using UV-spectrophotometer data. Approximately 26% of nanoparticles were recovered after drying. The percentage of total drug content was about 30%, and the percentage of drug entrapment reached 57%. Electrostatic Force Microscopy images confirmed the presence of gold inside the drug-loaded nanoparticles. We speculate that the 20-nm gold particles were able to diffuse, after 12 hours of mixing (using the roller mixer), into the PLGA matrix through the 100-nm pores (observed by SEM) without affecting the integrity of the drug delivery vehicle. These synthesized nanoparticles show promise as multimodal vehicles in the delivery of chemotherapeutic agents.

Polarizability of DNA block copolymer nanoparticles observed by electrostatic force microscopy.

In this study, DNA block copolymer (DBC) micelles with a polystyrene (PS) core and a single-stranded (ss) DNA shell were doped with ferrocene (Fc) molecules. Tapping mode atomic force microscopy (AFM) was used to study the morphology of the doped and undoped block copolymer aggregates. We show that introducing Fc molecules into the hydrophobic core does not affect the structural properties such as shape or size. In contrast, doping with Fc significantly changes the micelles' electrical properties, namely their polarizability. Electrostatic force microscopy (EFM) measurements reveal that the undoped micelles show no significant polarization signal, while the Fc-doped aggregates exhibit strongly enhanced polarizability. Furthermore, the nucleic acid moieties were utilized in combination with complementary ssDNA strands to assemble single particles into linear arrays of DBC nanoobjects. The ability to tune the electrostatic properties of the polymer core and the presence of nucleic acids might open the way for using these bioorganic nanoparticles as building blocks for nanoelectronic or biosensing devices.