Transition-Metal Decorated Aluminum Nanocrystals.

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into "antenna-reactor" heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics.

Optimization of Three-Dimensional (3D) Chemical Imaging by Soft X-Ray Spectro-Tomography Using a Compressed Sensing Algorithm.

Soft X-ray spectro-tomography provides three-dimensional (3D) chemical mapping based on natural X-ray absorption properties. Since radiation damage is intrinsic to X-ray absorption, it is important to find ways to maximize signal within a given dose. For tomography, using the smallest number of tilt series images that gives a faithful reconstruction is one such method. Compressed sensing (CS) methods have relatively recently been applied to tomographic reconstruction algorithms, providing faithful 3D reconstructions with a much smaller number of projection images than when conventional reconstruction methods are used. Here, CS is applied in the context of scanning transmission X-ray microscopy tomography. Reconstructions by weighted back-projection, the simultaneous iterative reconstruction technique, and CS are compared. The effects of varying tilt angle increment and angular range for the tomographic reconstructions are examined. Optimization of the regularization parameter in the CS reconstruction is explored and discussed. The comparisons show that CS can provide improved reconstruction fidelity relative to weighted back-projection and simultaneous iterative reconstruction techniques, with increasingly pronounced advantages as the angular sampling is reduced. In particular, missing wedge artifacts are significantly reduced and there is enhanced recovery of sharp edges. Examples of using CS for low-dose scanning transmission X-ray microscopy spectroscopic tomography are presented.

Crystal Face Distributions and Surface Site Densities of Two Synthetic Goethites: Implications for Adsorption Capacities as a Function of Particle Size.

Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on CrVI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.

Microfluidization of Graphite and Formulation of Graphene-Based Conductive Inks.

We report the exfoliation of graphite in aqueous solutions under high shear rate [∼ 108 s-1] turbulent flow conditions, with a 100% exfoliation yield. The material is stabilized without centrifugation at concentrations up to 100 g/L using carboxymethylcellulose sodium salt to formulate conductive printable inks. The sheet resistance of blade coated films is below ∼2Ω/□. This is a simple and scalable production route for conductive inks for large-area printing in flexible electronics.

Denoising time-resolved microscopy image sequences with singular value thresholding.

Time-resolved imaging in microscopy is important for the direct observation of a range of dynamic processes in both the physical and life sciences. However, the image sequences are often corrupted by noise, either as a result of high frame rates or a need to limit the radiation dose received by the sample. Here we exploit both spatial and temporal correlations using low-rank matrix recovery methods to denoise microscopy image sequences. We also make use of an unbiased risk estimator to address the issue of how much thresholding to apply in a robust and automated manner. The performance of the technique is demonstrated using simulated image sequences, as well as experimental scanning transmission electron microscopy data, where surface adatom motion and nanoparticle structural dynamics are recovered at rates of up to 32 frames per second.

Structural and Optical Properties of Discrete Dendritic Pt Nanoparticles on Colloidal Au Nanoprisms.

Catalytic and optical properties can be coupled by combining different metals into nanoscale architectures in which both the shape and the composition provide fine-tuning of functionality. Here, discrete, small Pt nanoparticles (diameter = 3-6 nm) were grown in linear arrays on Au nanoprisms, and the resulting structures are shown to retain strong localized surface plasmon resonances. Multidimensional electron microscopy and spectroscopy techniques (energy-dispersive X-ray spectroscopy, electron tomography, and electron energy-loss spectroscopy) were used to unravel their local composition, three-dimensional morphology, growth patterns, and optical properties. The composition and tomographic analyses disclose otherwise ambiguous details of the Pt-decorated Au nanoprisms, revealing that both pseudospherical protrusions and dendritic Pt nanoparticles grow on all faces of the nanoprisms (the faceted or occasionally twisted morphologies of which are also revealed), and shed light on the alignment of the Pt nanoparticles. The electron energy-loss spectroscopy investigations show that the Au nanoprisms support multiple localized surface plasmon resonances despite the presence of pendant Pt nanoparticles. The plasmonic fields at the surface of the nanoprisms indeed extend into the Pt nanoparticles, opening possibilities for combined optical and catalytic applications. These insights pave the way toward comprehensive nanoengineering of multifunctional bimetallic nanostructures, with potential applications in plasmon-enhanced catalysis and in situ monitoring of chemical processes via surface-enhanced spectroscopy.

Merging Single-Atom-Dispersed Silver and Carbon Nitride to a Joint Electronic System via Copolymerization with Silver Tricyanomethanide.

Herein, we present an approach to create a hybrid between single-atom-dispersed silver and a carbon nitride polymer. Silver tricyanomethanide (AgTCM) is used as a reactive comonomer during templated carbon nitride synthesis to introduce both negative charges and silver atoms/ions to the system. The successful introduction of the extra electron density under the formation of a delocalized joint electronic system is proven by photoluminescence measurements, X-ray photoelectron spectroscopy investigations, and measurements of surface ζ-potential. At the same time, the principal structure of the carbon nitride network is not disturbed, as shown by solid-state nuclear magnetic resonance spectroscopy and electrochemical impedance spectroscopy analysis. The synthesis also results in an improvement of the visible light absorption and the development of higher surface area in the final products. The atom-dispersed AgTCM-doped carbon nitride shows an enhanced performance in the selective hydrogenation of alkynes in comparison with the performance of other conventional Ag-based materials prepared by spray deposition and impregnation-reduction methods, here exemplified with 1-hexyne.

Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations.

Compressed sensing electron tomography of needle-shaped biological specimens--Potential for improved reconstruction fidelity with reduced dose.

Electron tomography is an invaluable method for 3D cellular imaging. The technique is, however, limited by the specimen geometry, with a loss of resolution due to a restricted tilt range, an increase in specimen thickness with tilt, and a resultant need for subjective and time-consuming manual segmentation. Here we show that 3D reconstructions of needle-shaped biological samples exhibit isotropic resolution, facilitating improved automated segmentation and feature detection. By using scanning transmission electron tomography, with small probe convergence angles, high spatial resolution is maintained over large depths of field and across the tilt range. Moreover, the application of compressed sensing methods to the needle data demonstrates how high fidelity reconstructions may be achieved with far fewer images (and thus greatly reduced dose) than needed by conventional methods. These findings open the door to high fidelity electron tomography over critically relevant length-scales, filling an important gap between existing 3D cellular imaging techniques.

The Dark Side of EDX Tomography: Modeling Detector Shadowing to Aid 3D Elemental Signal Analysis.

A simple model is proposed to account for the loss of collected X-ray signal by the shadowing of X-ray detectors in the scanning transmission electron microscope. The model is intended to aid the analysis of three-dimensional elemental data sets acquired using energy-dispersive X-ray tomography methods where shadow-free specimen holders are unsuitable or unavailable. The model also provides a useful measure of the detection system geometry.

Three-dimensional imaging of localized surface plasmon resonances of metal nanoparticles.

The remarkable optical properties of metal nanoparticles are governed by the excitation of localized surface plasmon resonances (LSPRs). The sensitivity of each LSPR mode, whose spatial distribution and resonant energy depend on the nanoparticle structure, composition and environment, has given rise to many potential photonic, optoelectronic, catalytic, photovoltaic, and gas- and bio-sensing applications. However, the precise interplay between the three-dimensional (3D) nanoparticle structure and the LSPRs is not always fully understood and a spectrally sensitive 3D imaging technique is needed to visualize the excitation on the nanometre scale. Here we show that 3D images related to LSPRs of an individual silver nanocube can be reconstructed through the application of electron energy-loss spectrum imaging, mapping the excitation across a range of orientations, with a novel combination of non-negative matrix factorization, compressed sensing and electron tomography. Our results extend the idea of substrate-mediated hybridization of dipolar and quadrupolar modes predicted by theory, simulations, and electron and optical spectroscopy, and provide experimental evidence of higher-energy mode hybridization. This work represents an advance both in the understanding of the optical response of noble-metal nanoparticles and in the probing, analysis and visualization of LSPRs.

Compressed sensing electron tomography.

The recent mathematical concept of compressed sensing (CS) asserts that a small number of well-chosen measurements can suffice to reconstruct signals that are amenable to sparse or compressible representation. In addition to powerful theoretical results, the principles of CS are being exploited increasingly across a range of experiments to yield substantial performance gains relative to conventional approaches. In this work we describe the application of CS to electron tomography (ET) reconstruction and demonstrate the efficacy of CS-ET with several example studies. Artefacts present in conventional ET reconstructions such as streaking, blurring of object boundaries and elongation are markedly reduced, and robust reconstruction is shown to be possible from far fewer projections than are normally used. The CS-ET approach enables more reliable quantitative analysis of the reconstructions as well as novel 3D studies from extremely limited data.

A new approach to the investigation of nanoparticles: electron tomography with compressed sensing.

The principal purpose of this contribution is to illustrate the potential of compressed sensing electron tomography for the characterisation of nanoparticulate materials that are vulnerable to electron beam damage. Not only is there growing interest in nanoparticles of organic materials in medical and allied contexts, there is also the need to investigate nanoparticles and nanoclusters of metals supported on biological macromolecular entities in the context of drug delivery. A qualitative account of the principles of electron tomography is outlined with illustrations from the field of heterogeneous catalysis, where electron beam damage is less of an issue, and an appendix deals with more quantitative aspects of how compressed sensing promises to expand the range of samples that have hitherto been accessible to investigation.

Recent advances in the application of electron tomography to materials chemistry.

Nowadays, tomography plays a central role in pureand applied science, in medicine, and in many branches of engineering and technology. It entails reconstructing the three-dimensional (3D) structure of an object from a tilt series of two-dimensional (2D) images. Its origin goes back to 1917, when Radon showed mathematically how a series of 2D projection images could be converted to the 3D structural one. Tomographic X-ray and positron scanning for 3D medical imaging, with a resolution of ∼1 mm, is now ubiquitous in major hospitals. Electron tomography, a relatively new chemical tool, with a resolution of ∼1 nm, has been recently adopted by materials chemists as an invaluable aid for the 3D study of the morphologies, spatially-discriminating chemical compositions, and defect properties of nanostructured materials. In this Account, we review the advances that have been made in facilitating the recording of the required series of 2D electron microscopic images and the subsequent process of 3D reconstruction of specimens that are vulnerable, to a greater or lesser degree, to electron beam damage. We describe how high-fidelity 3D tomograms may be obtained from relatively few 2D images by incorporating prior structural knowledge into the reconstruction process. In particular, we highlight the vital role of compressed sensing, a recently developed procedure well-known to information theorists that exploits ideas of image compression and "sparsity" (that the important image information can be captured in a reduced data set). We also touch upon another promising approach, "discrete" tomography, which builds into the reconstruction process a prior assumption that the object can be described in discrete terms, such as the number of constituent materials and their expected densities. Other advances made recently that we outline, such as the availability of aberration-corrected electron microscopes, electron wavelength monochromators, and sophisticated specimen goniometers, have all contributed significantly to the further development of quantitative 3D studies of nanostructured materials, including nanoparticle-heterogeneous catalysts, fuel-cell components, and drug-delivery systems, as well as photovoltaic and plasmonic devices, and are likely to enhance our knowledge of many other facets of materials chemistry, such as organic-inorganic composites, solar-energy devices, bionanotechnology, biomineralization, and energy-storage systems composed of high-permittivity metal oxides.

Three-dimensional morphology of iron oxide nanoparticles with reactive concave surfaces. A compressed sensing-electron tomography (CS-ET) approach.

In this paper, we apply electron tomography (ET) to the study of the three-dimensional (3D) morphology of iron oxide nanoparticles (NPs) with reactive concave surfaces. The ability to determine quantitatively the volume and shape of the NP concavity is essential for understanding the key-lock mechanism responsible for the destabilization of gold nanocrystals within the iron oxide NP concavity. We show that quantitative ET is enhanced greatly by the application of compressed sensing (CS) techniques to the tomographic reconstruction. High-fidelity tomograms using a new CS-ET algorithm reveal with clarity the concavities of the particle and enable 3D nanometrology studies to be undertaken with confidence. In addition, the robust performance of the CS-ET algorithm with undersampled data should allow rapid progress with time-resolved 3D nanoscale studies, 3D atomic resolution imaging, and cryo-tomography of nanoscale cellular structures.