RESUMEN
Nanosized metal aggregates (MAs), including metal nanoparticles (NPs) and nanoclusters (NCs), are often the active species in numerous applications. In order to maintain the active form of MAs in "use", they need to be anchored and stabilised, preventing agglomeration. In this context, metal-organic frameworks (MOFs), which exhibit a unique combination of properties, are of particular interest as a tunable and porous matrix to host MAs. A high degree of control in the synthesis towards atom-efficient and application-oriented MA@MOF composites is required to derive specific structure-property relationships and in turn to enable design of functions on the molecular level. Due to the versatility of MA@MOF (derived) materials, their applications are not limited to the obvious field of catalysis, but increasingly include 'out of the box' applications, for example medical diagnostics and theranostics, as well as specialised (bio-)sensoring techniques. This review focuses on recent advances in the controlled synthesis of MA@MOF materials en route to atom-precise MAs. The main synthetic strategies, namely 'ship-in-bottle', 'bottle-around-ship', and approaches to achieve novel hierarchical MA@MOF structures are highlighted and discussed while identifying their potential as well as their limitations. Hereby, an overview of standard characterisation methods that enable a systematic analysis procedure and state-of-art techniques that localise MA within MOF cavities are provided. While the perspectives of MA@MOF materials in general have been reviewed various times in the recent past, few atom-precise MAs inside MOFs have been reported so far, opening opportunities for future investigation.
Asunto(s)
Estructuras Metalorgánicas , Estructuras Metalorgánicas/química , Catálisis , Porosidad , MetalesRESUMEN
Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ([Formula: see text]) is less than the average [Formula: see text] supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO[Formula: see text] V[Formula: see text]O[Formula: see text] V[Formula: see text]O[Formula: see text].
RESUMEN
Studies on materials affected by large thermal gradients and rapid thermal cycling are an area of increasing interest, driving the need for real time observations of microstructural evoultion under transient thermal conditions. However, current in situ transmission electron microscope (TEM) heating stages introduce uniform temperature distributions across the material during heating experiments. Here, a methodology is described to generate thermal gradients across a TEM specimen by modifying a commercially available MEMS-based heating stage. It was found that a specimen placed next to the metallic heater, over a window, cut by FIB milling, does not disrupt the overall thermal stability of the device. Infrared thermal imaging (IRTI) experiments were performed on unmodified and modified heating devices, to measure thermal gradients across the device. The mean temperature measured within the central viewing area of the unmodified device was 3-5% lower than the setpoint temperature. Using IRTI data, at setpoint temperatures ranging from 900 to 1,300°C, thermal gradients at the edge of the modified window were calculated to be in the range of 0.6 × 106 to 7.0 × 106 °C/m. Additionally, the Ag nanocube sublimation approach was used, to measure the local temperature across a FIB-cut Si lamella at high spatial resolution inside the TEM, and demonstrate "proof of concept" of the modified MEMS device. The thermal gradient across the Si lamella, measured using the latter approach was found to be 6.3 × 106 °C/m, at a setpoint temperature of 1,000°C. Finally, the applicability of this approach and choice of experimental parameters are critically discussed.
RESUMEN
Ni based catalysts have been widely studied for H2 production due to the ability of Ni to break C-C and C-H bonds. In this work, we study inverse catalysts prepared by well-controlled sub-monolayer deposition of CeO2 nanocubes onto Ni thin films for ethanol steam reforming (ESR). Results show that controlling the coverage of CeO2 nanocubes on Ni enhances H2 production by more than an order of magnitude compared to pure Ni. Contrary to the idea that C deposits must be continuously oxidized for sustained H2 production, the surface of the most active catalysts show significant C deposition, yet no deactivation is observed. HAADF-STEM analysis reveals the formation of carbon filaments (CFILs), which propel Ni particles upward at the filament tips via a catalytic tip growth mechanism, resulting in a Ni@CFIL active phase for ESR. Near-ambient pressure XPS indicates that the Ni@CFIL active phase forms as a result of C gradients at the interface between regions of pure Ni metal and domains of closely packed CeO2 nanocubes. These results show that the mesoscale morphology of deposited CeO2 nanocubes is responsible for templating the formation of a Ni@CFIL catalyst, which resists deactivation leading to highly active and stable H2 production from ethanol.
RESUMEN
It is well known that an excess of hydroxyl radicals (ËOH) in the human body is responsible for oxidative stress-related diseases. An understanding of the relationship between the concentration of ËOH and those diseases could contribute to better diagnosis and prevention. Here we present a supersensitive nanosensor integrated with an electrochemical method to measure the concentration of ËOH in vitro. The electrochemical sensor consists of a composite comprised of ultrasmall cerium oxide nanoclusters (<2 nm) grafted to a highly conductive carbon deposited on a screen-printed carbon electrode (SPCE). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to analyze the interaction between cerium oxide nanoclusters and ËOH. The CV results demonstrated that this electrochemical sensor had the capacity of detecting ËOH with a high degree of accuracy and selectivity, achieving a consistent performance. Additionally, EIS results confirmed that our electrochemical sensor was able to differentiate ËOH from hydrogen peroxide (H2O2), which is another common reactive oxygen species (ROS) found in the human body. The limit of detection (LOD) observed with this electrochemical sensor was of 0.6 µM. Furthermore, this nanosized cerium oxide-based electrochemical sensor successfully detected in vitro the presence of ËOH in preosteoblast cells from newborn mouse bone tissue. The supersensitive electrochemical sensor is expected to be beneficially used in multiple applications, including medical diagnosis, fuel-cell technology, and food and cosmetic industries.
Asunto(s)
Peróxido de Hidrógeno , Nanocompuestos , Animales , Técnicas Electroquímicas , Electrodos , Límite de Detección , RatonesRESUMEN
Micro-electro-mechanical systems (MEMS)-based heating holders offer exceptional control of temperature and heating/cooling rates for transmission electron microscopy experiments. The use of such devices is relatively straightforward for nano-particulate samples, but the preparation of specimens from bulk samples by focused ion beam (FIB) milling presents significant challenges. These include: poor mechanical integrity and site selectivity of the specimen, ion beam damage to the specimen and/or MEMS device during thinning, and difficulties in transferring the specimen onto the MEMS device. Here, we describe a novel FIB protocol for the preparation and transfer of specimens from bulk samples, which involves a specimen geometry that provides mechanical support to the electron-transparent region, while maximizing the area of that region and the contact area with the heater plate on the MEMS chip. The method utilizes an inclined stage block that minimizes exposure of the chip to the ion beam during milling. This block also allows for accurate and gentle placement of the FIB-cut specimen onto the chip by using simultaneous electron and ion beam imaging during transfer. Preliminary data from Si and Ag on Si samples are presented to demonstrate the quality of the specimens that can be obtained and their stability during in situ heating experiments.
RESUMEN
The introduction of scanning/transmission electron microscopes (S/TEM) with sub-Angstrom resolution as well as fast and sensitive detection solutions support direct observation of dynamic phenomena in-situ at the atomic scale. Thereby, in-situ specimen holders play a crucial role: accurate control of the applied in-situ stimulus on the nanostructure combined with the overall system stability to assure atomic resolution are paramount for a successful in-situ S/TEM experiment. For those reasons, MEMS-based TEM sample holders are becoming one of the preferred choices, also enabling a high precision in measurements of the in-situ parameter for more reproducible data. A newly developed MEMS-based microheater is presented in combination with the new NanoEx™-i/v TEM sample holder. The concept is built on a four-point probe temperature measurement approach allowing active, accurate local temperature control as well as calorimetry. In this paper, it is shown that it provides high temperature stability up to 1,300°C with a peak temperature of 1,500°C (also working accurately in gaseous environments), high temperature measurement accuracy (<4%) and uniform temperature distribution over the heated specimen area (<1%), enabling not only in-situ S/TEM imaging experiments, but also elemental mapping at elevated temperatures using energy-dispersive X-ray spectroscopy (EDS). Moreover, it has the unique capability to enable simultaneous heating and biasing experiments.
RESUMEN
Transmission electron microscopy (TEM) in combination with electron tomography is widely used to obtain nanometer scale three-dimensional (3D) structural information about biological samples. However, studies of whole eukaryotic cells are limited in resolution and/or contrast on account of the effect of chromatic aberration of the TEM objective lens on electrons that have been scattered inelastically in the specimen. As a result, 3D information is usually obtained from sections and not from whole cells. Here, we use chromatic aberration-corrected TEM to record bright-field TEM images of nanoparticles in a whole mount macrophage cell. Tilt series of images are used to generate electron tomograms, which are analyzed to assess the spatial resolution that can be achieved for different vertical positions in the specimen. The uptake of gold nanoparticles coated with low-density lipoprotein (LDL) is studied. The LDL is found to assemble in clusters. The clusters contain nanoparticles taken up on different days, which are joined without mixing their nanoparticle cargo.
Asunto(s)
Tomografía con Microscopio Electrónico/métodos , Procesamiento de Imagen Asistido por Computador/métodos , Macrófagos/metabolismo , Macrófagos/ultraestructura , Nanopartículas/metabolismo , Nanopartículas/ultraestructura , Línea Celular , Oro/metabolismo , Humanos , FagocitosisRESUMEN
Until now it has not been possible to image at atomic resolution using classical electron tomographic methods, except when the target is a perfectly crystalline nano-object imaged along a few zone axes. The main reasons are that mechanical tilting in an electron microscope with sub-ångström precision over a very large angular range is difficult, that many real-life objects such as dielectric layers in microelectronic devices impose geometrical constraints and that many radiation-sensitive objects such as proteins limit the total electron dose. Hence, there is a need for a new tomographic scheme that is able to deduce three-dimensional information from only one or a few projections. Here we present an electron tomographic method that can be used to determine, from only one viewing direction and with sub-ångström precision, both the position of individual atoms in the plane of observation and their vertical position. The concept is based on the fact that an experimentally reconstructed exit wave consists of the superposition of the spherical waves that have been scattered by the individual atoms of the object. Furthermore, the phase of a Fourier component of a spherical wave increases with the distance of propagation at a known 'phase speed'. If we assume that an atom is a point-like object, the relationship between the phase and the phase speed of each Fourier component is linear, and the distance between the atom and the plane of observation can therefore be determined by linear fitting. This picture has similarities with Big Bang cosmology, in which the Universe expands from a point-like origin such that the distance of any galaxy from the origin is linearly proportional to the speed at which it moves away from the origin (Hubble expansion). The proof of concept of the method has been demonstrated experimentally for graphene with a two-layer structure and it will work optimally for similar layered materials, such as boron nitride and molybdenum disulphide.
RESUMEN
Understanding how molecules can restructure the surfaces of heterogeneous catalysts under reaction conditions requires methods that can visualize atoms in real space and time. We applied a newly developed aberration-corrected environmental transmission electron microscopy to show that adsorbed carbon monoxide (CO) molecules caused the {100} facets of a gold nanoparticle to reconstruct during CO oxidation at room temperature. The CO molecules adsorbed at the on-top sites of gold atoms in the reconstructed surface, and the energetic favorability of this reconstructed structure was confirmed by ab initio calculations and image simulations. This atomic-scale visualizing method can be applied to help elucidate reaction mechanisms in heterogeneous catalysis.
RESUMEN
We have observed a previously undescribed stepwise oxidation of mono- and few layer suspended graphene by silver nanoparticles in situ at subnanometer scale in an environmental transmission electron microscope. Over the range of 600-850 K, we observe crystallographically oriented channelling with rates in the range 0.01-1 nm/s and calculate an activation energy of 0.557 ± 0.016 eV. We present a discrete statistical model for this process and discuss the implications for accurate nanoscale patterning of nanoscale systems.
Asunto(s)
Grafito/química , Nanopartículas del Metal/química , Plata/química , Termodinámica , Microscopía Electrónica de Transmisión , Nanotecnología , Oxidación-Reducción , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
Carbon nanotubes (CNTs) are being investigated for a variety of biomedical applications. Despite numerous studies, the pathways by which carbon nanotubes enter cells and their subsequent intracellular trafficking and distribution remain poorly determined. Here, we use 3-D electron tomography techniques that offer optimum enhancement of contrast between carbon nanotubes and the plasma membrane to investigate the mechanisms involved in the cellular uptake of shortened, functionalised multi-walled carbon nanotubes (MWNT-NH(3)(+)). Both human lung epithelial (A549) cells, that are almost incapable of phagocytosis and primary macrophages, capable of extremely efficient phagocytosis, were used. We observed that MWNT-NH(3)(+) were internalised in both phagocytic and non-phagocytic cells by any one of three mechanisms: (a) individually via membrane wrapping; (b) individually by direct membrane translocation; and (c) in clusters within vesicular compartments. At early time points following intracellular translocation, we noticed accumulation of nanotube material within various intracellular compartments, while a long-term (14-day) study using primary human macrophages revealed that MWNT-NH(3)(+) were able to escape vesicular (phagosome) entrapment by translocating directly into the cytoplasm.
Asunto(s)
Carbono/química , Carbono/farmacocinética , Tomografía con Microscopio Electrónico/métodos , Imagenología Tridimensional/métodos , Nanotubos de Carbono/química , Fagocitosis/fisiología , Línea Celular Tumoral , Membrana Celular/química , Membrana Celular/metabolismo , Citoplasma/química , Citoplasma/metabolismo , Humanos , Macrófagos/química , Macrófagos/metabolismo , Fagosomas/química , Fagosomas/metabolismoRESUMEN
Hard-magnetic nanomaterials like nanoparticles of FePt are of great interest because of their promising potential for data storage applications. The magnetic properties of FePt structures strongly differ whether the crystal phases are face centered cubic (fcc) or face centered tetragonal (fct). We evaluated aberration corrected HRTEM, electron diffraction and aberration corrected HAADF-STEM as methods to measure the chemical degree of order S that describes the ordering of Pt and Fe atoms within the crystals unit cells. S/TEM experiments are accompanied by image calculations. The findings are compared with results obtained from X-ray diffraction on a FePt film. Our results show that STEM is a reasonable fast approach over HRTEM and electron diffraction to locally determine the chemical degree of order S.
RESUMEN
Electrochromic Ruthenium Purple-polymer nanocomposite films, fabricated by multilayer assembly, were found to exhibit sub-second switching speed and the highest electrochromic contrast reported to date for any inorganic material.
RESUMEN
A method is presented for retrieving the variation of the absorptive potential in electron beam sensitive soft material. The absorptive potential is directly related to the variations in atomic density and in chemical composition fluctuation. In our approach only a single zero-loss energy-filtered bright-field transmission electron microscopy (TEM) image is sufficient to obtain this information. The accuracy and the effectiveness of this proposed method has been tested using both simulation and experiment. As an experimental example of soft (organic) material, the variation in absorptive potential in an unstained tissue sample of zebrafish gill has been determined.
Asunto(s)
Branquias/ultraestructura , Microscopía Electrónica de Transmisión de Rastreo/instrumentación , Animales , Microscopía Electrónica de Transmisión de Rastreo/métodos , Pez CebraRESUMEN
The discovery that negatively charged aggregates of C60 fullerene are stable in aqueous environments has elicited concerns regarding the potential environmental and health effects of these aggregates. Many previous studies have used aggregates synthesized using intermediate organic solvents. This work primarily employed an aggregate production method that more closely emulates the fate of C60 upon accidental release into the environment: extended mixing in water. The aggregates formed via this method (aqu/nC60) differ from those produced using the more common solvent exchange methods. The aqu/nC60 aggregates are heterogeneous in size (20 nm and larger) and shape (facetted to spherical), negatively charged, and crystalline in structure, exhibiting a face centered cubic (FCC) system. Solution characteristics such as aqu/nC60 aggregate size and concentration were found to be dependent upon preparation variables such as initial C60 concentration, initial particle size, and the presence or absence of natural organic matter. These results indicate that care should be taken when attempting to compare experimental results obtained with aqu/nC60 to nC60 produced by solvent exchange methods.
Asunto(s)
Fulerenos/química , Contaminantes Químicos del Agua/química , Coloides , Cristalización , Microscopía Electrónica de Transmisión , Nanopartículas/química , Nanopartículas/ultraestructura , Tamaño de la Partícula , Espectrofotometría Ultravioleta , Propiedades de SuperficieRESUMEN
We present a simple, fast, and practical route to vertically align carbon nanotubes on a porous support using a combination of self-assembly and filtration methods. The advantage of this approach is that it can be easily scaled up to large surface areas, allowing the fabrication of membranes for practical gas separation applications. The gas transport properties of thus constructed nanotube/polymer nanocomposite membranes are analogous to those of carbon nanotube membranes grown by chemical vapor deposition. This paper shows the first data for transport of gas mixtures through carbon nanotube membranes. The permeation of gas mixtures through the membranes exhibits different properties than those observed using single-gas experiments, confirming that non-Knudsen transport occurs.