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A new bismuth metal–organic framework (MOF), bismuth-NU-901 (Bi-NU-901), featuring the scu topology and a pore with a diameter of ∼11 A, was solvothermally synthesized, and its use as an X-ray comp...

Covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, the utilization of redox-active sites embedded within COFs is often limited by the low intrinsic conductivities of bulk-grown material, resulting in poor electrochemical performance. Here, a general strategy is developed to improve the energy storage capability of COF-based electrodes by integrating COFs with carbon nanotubes (CNT). These COF composites feature an abundance of redox-active 2,7-diamino-9,10-phenanthrenequinone (DAPQ) based motifs, robust β‑ketoenamine linkages, and well-defined mesopores. The composite materials (DAPQ-COFX—where X = wt% of CNT) are prepared by in situ polycondensation and have tube-type core-shell structures with intimately grown COF layers on the CNT surface. This synergistic structural design enables superior electrochemical performance: DAPQ-COF50 shows 95% utilization of redox-active sites, long cycling stability (76% retention after 3000 cycles at 2000 mA g−1), and ultra-high rate capability, with 58% capacity retention at 50 A g−1. This rate translates to charging times of ≈11 s (320 C), implying that DAPQ-COF50 holds excellent promise for high-power cells. Furthermore, the rate capability outperformed all previous reports for carbonyl-containing organic electrodes by an order of magnitude; indeed, this power density and the rapid (dis)charge time are competitive with electrochemical capacitors.

Ethane oxidative dehydrogenation (ODH) is an alternative route for ethene production. Crystalline M1 phase of Mo-V mixed metal oxide is an excellent catalyst for this reaction. Here we show a hydrothermal synthesis method that generates M1 phases with high surface areas starting from poorly soluble metal oxides. Use of organic additives allows control of the concentration of metals in aqueous suspension. Reactions leading to crystalline M1 take place at 190 °C, i.e., approximately 400 °C lower than under current synthesis conditions. The evolution of solvated polyoxometalate ions and crystalline phases in the solid is monitored by spectroscopies. Catalysts prepared by this route show higher ODH activity compared to conventionally prepared catalysts. The higher activity is due not only to the high specific surface area but also to the corrugated lateral termination of the M1 crystals, as seen by atomic resolution electron microscopy, exposing a high concentration of catalytically active sites., Crystalline M1 phase of Mo-V-Te-Nb mixed oxide is an excellent catalyst for ethane oxidative dehydrogenation to ethene. Here, the authors show a method that synthesizes highly active materials by generating M1 crystals with corrugated terminations, thus exposing a large concentration of active sites.

Most covalent organic frameworks (COFs) are synthesized using solvothermal conditions (>120 °C, >72 h) in harmful organic solvents. We report a strategy for rapidly synthesizing imine-linked COFs (< 60 min) in aqueous acetic acid using sonochemistry, avoiding most of the downsides of solvothermal methods. We first synthesized seven known COFs using this method and obtained crystallinity and porosity comparable to or better than materials from previously reported solvothermal routes. This sonochemical method even works in highly sustainable solvents, such as food-grade vinegar. The generality of the method was demonstrated by preparing two unreported COFs. Finally, we showed that one sonochemical COF is an excellent photocatalyst for sacrificial hydrogen evolution from water with a more sustained catalytic performance than its solvothermal analog. The speed, ease and generality of this sonochemical method with no sacrifice in material quality makes it an enabling methodology for rapid discovery of new functional COF materials.

A major challenge for lithium-ion batteries based on nickel-rich layered oxide cathodes is capacity fading. While chemo-mechanical degradation and/or structural transformation are widely considered responsible for degradation, a comprehensive understanding of this process is still not complete. For the stable performance of these cathode materials, aluminium (Al) plays a crucial role, not only as a current collector but also as substitutional element for the transition metals in the cathodes and a protective oxide coating (as Al2O3). However, excess Al can be detrimental due to both its redox inactive nature in the cathode and the insulating nature of Al2O3. In this work, we report an analysis of the Al content in two different types of nickel-rich manganese cobalt oxide cathode materials after battery cycling. Our results indicate a significant thickening of Al-containing phases on the surface of the NMC811 electrode. Similar results are observed from commercial batteries (a mixture of NMC532 and LiMn2O4) that were analysed before use and at the end of life, where Al-containing phases were found to increase significantly at surfaces and grain boundaries. Considering the detrimental effects of the excess Al in the nickel-rich cathodes, our observation of increased Al content via battery cycling is believed to bring a new perspective to the ongoing discussions regarding the capacity fading phenomenon of nickel-rich layered oxide materials as part of their complex degradation mechanisms.

Perpendicular magnetic anisotropy (PMA) has recently been shown to emerge at interfaces of 3d and 5d transition-metal oxides (TMOs). However, strategies to systematically stabilize such interface-driven PMA still remains elusive, hindering further applications of this design approach. Here, tuning crystal symmetry is shown to be an effective means to engineer this interfacial phenomenon. The evolution of PMA strength as a function of ferromagnetic oxide thickness quantitatively reveals the competition between volume- and interface-specific contributions that determine the magnetic anisotropy. By applying different degrees of epitaxial strain, the relative contributions to PMA are modulated, clearly revealing their correlations with crystal symmetries. To be more specific, the volume anisotropy energy is found to be correlated with the tetragonal distortion of the ferromagnetic layer, while the interface anisotropy energy is mainly modulated by the octahedral tilting at the interface. With these insights, superlattices with enhanced interface-driven PMA and higher Curie temperature are realized. These findings reveal a route to engineering interface-driven PMA and associated magnetic phenomena in TMO heterostructures for future spintronic applications.

Nanostructured materials have interesting optical and electronic properties that are often drastically different from those of their bulk counterparts. While bulk organic/inorganic semiconductor composites have attracted much attention in the past decade, the preparation of organic/inorganic semiconductor nanocomposites (OISNs) still remains challenging. This work presents an assembly method for the co-encapsulation of titanium dioxide dots (TDs) with a cyano-substituted soluble conjugated polymer (CSCP) into a particular nanoparticle. The as-prepared CSCP/TD semiconductor nanocomposites (CSCP/TD NCs) exhibit different particle surfaces and morphologies depending on the mass ratio of the CSCP to TDs. We then tested them as photocatalysts for sacrificial hydrogen production from water. We found that nanocomposites outperformed nanoparticles of the individual components and physical mixtures thereof. The most active CSCP/TD NC had a catalytic H2 production rate that was 4.25 times higher than that of pure polymer nanoparticles prepared under the same conditions. We ascribe this to energy transfer between the semiconductors, where direct phase contact is essential, highlighting a potential avenue for using soluble, visible light-absorbing conjugated organic polymers to build Z-schemes for overall water splitting in the future.

Beam damage caused during acquisition of the highest resolution images is the current limitation in the vast majority of experiments performed in a scanning transmission electron microscope (STEM). While the principles behind the processes of knock-on and radiolysis damage are well-known (as are other contributing effects, such as heat and electric fields), understanding how and especially when beam damage is distributed across the entire sample volume during an experiment has not been examined in detail. Here we use standard models for damage and diffusion to elucidate how beam damage spreads across the sample as a function of the microscope conditions to determine an "optimum" sampling approach that maximises the high-resolution information in any image acquisition. We find that the standard STEM approach of scanning an image sequentially accelerates damage because of increased overlap of diffusion processes. These regions of accelerated damage can be significantly decelerated by increasing the distance between the acquired pixels in the scan, forming a "spotscan" mode of acquisition. The optimum distance between these pixels can be broadly defined by the fundamental properties of each material, allowing experiments to be designed for specific beam sensitive materials. As an added bonus, if we use inpainting to reconstruct the sparse distribution of pixels in the image we can significantly increase the speed of the STEM process, allowing dynamic phenomena, and the onset of damage, to be studied directly.

Insights into the dynamics of electrochemical processes are critically needed to improve our fundamental understanding of electron, charge, and mass transfer mechanisms and reaction kinetics that influence a broad range of applications, from the functionality of electrical energy-storage and conversion devices (e.g., batteries, fuel cells, and supercapacitors), to materials degradation issues (e.g., corrosion and oxidation), and materials synthesis (e.g., electrodeposition). To unravel these processes, in situ electrochemical scanning/transmission electron microscopy (ec-S/TEM) was developed to permit detailed site-specific characterization of evolving electrochemical processes that occur at electrode–electrolyte interfaces in their native electrolyte environment, in real time and at high-spatial resolution. This approach utilizes “closed-form” microfabricated electrochemical cells that couple the capability for quantitative electrochemical measurements with high spatial and temporal resolution imaging, spectroscopy, and diffraction. In this article, we review the state-of-the-art instrumentation for in situ ec-S/TEM and how this approach has resulted in new observations of electrochemical processes.

Electrodeposition is widely used to fabricate tunable nanostructured materials in applications ranging from biosensing to energy conversion. A model based on 3D island growth is widely accepted in the explanation of the initial stages of nucleation and growth in electrodeposition. However, there are regions in the electrodeposition parameter space where this model becomes inapplicable. We use liquid cell transmission electron microscopy along with post situ scanning electron microscopy to investigate electrodeposition in this parameter space, focusing on the effect of the supporting electrolyte, and to shed light on the nucleation and growth of palladium. Using a collection of electron microscopy images and current time transients recorded during electrodeposition, we discover that electrochemical aggregative growth, rather than 3D island growth, best describes the electrodeposition process. We then use this model to explain the change in the morphology of palladium electrodeposits from spherical to open clusters with nonspherical morphology when HCl is added to the electrolyte solution. The enhanced understanding of the early stages of palladium nucleation and growth and the role of electrolyte in this process provides a systematic route toward the electrochemical fabrication of nanostructured materials.

We have explored the effect of magnetic rare-earth dopants substitutionally incorporated on the Ba sites of ${\mathrm{BaSnO}}_{3}$ in terms of electronic transport, magnetism, and optical properties. We show that for ${\mathrm{Ba}}_{0.92}{R}_{0.08}{\mathrm{SnO}}_{3}$ thin films (where $R=\text{La,}\phantom{\rule{4.pt}{0ex}}\text{Pr,}\phantom{\rule{4.pt}{0ex}}\text{Nd,}\phantom{\rule{4.pt}{0ex}}\text{Gd}$), there is a linear increase of mobility with carrier concentration across all doping schemes. La-doped films have the highest mobilities, followed by Pr- and Nd-doped films. Gd-doped samples have the largest ionic size mismatch with the Ba site and correspondingly the lowest carrier concentrations and electron mobilities. However, crystallinity does not appear to be a strong predictor of transport phenomena; our results suggest that point defects more than grain boundaries are key ingredients in tuning the conduction of ${\mathrm{BaSnO}}_{3}$ films grown by pulsed laser deposition. Pronounced, nonhysteretic x-ray magnetic dichroism signals are observed for Pr-, Nd-, and Gd-doped samples, indicating paramagnetism. Finally, we probe the optical constants for each of the ${\mathrm{BaSnO}}_{3}$ doping schemes and note that there is little change in the transmittance across all samples. Together these results shed light on conduction mechanisms in ${\mathrm{BaSnO}}_{3}$ doped with rare-earth cations.

Through solar, wind, or geothermal reallocation sources, heat transformation via adsorption-based systems provides the means to address the high energy global demand from refrigeration and cooling. However, improvements toward a suitable, high performing adsorbent–refrigerant working pair must be made to boost the applicability of such systems. For the first time, a series of mesoporous metal–organic frameworks (MOFs) have been tested for R134a fluorocarbon adsorption for this purpose. Each of the selected MOFs exhibit excellent, reversible R134a adsorption. Among them, NU-1000 provided an exceptional fluorocarbon uptake of ∼170 wt % near saturation, which is among the highest values reported so far for MOFs. Exhibiting appropriate equilibrium isotherm behavior and working capacities as large as 125 wt %, it is evident that mesoporous MOFs—especially those with hierarchical structure—are promising candidates for chiller applications. Such high performance materials provide significant potential for the de...

Developing the ability to synthesize compositionally and morphologically well-defined gibbsite particles with high yield is an ongoing need that has not yet achieved the required level of rational design. Here we report optimization of a clean inorganic synthesis route based on statistical experimental design examining the influence of Al(OH)3 gel precursor concentration, pH, and aging time at temperature. At 80 °C, the optimum synthesis conditions of gel concentration at 0.5 M, pH at 9.2, and time at 72 h maximized the reaction yield up to ∼88%. The resulting gibbsite product is composed of highly uniform euhedral hexagonal nanoplates within a basal plane diameter range of 200–400 nm. The independent roles of key system variables in the growth mechanism are considered. On the basis of these optimized experimental conditions, the synthesis procedure, which is both cost-effective and environmentally friendly, has the potential for mass production scale-up of high quality gibbsite material for various funda...

The discovery of emergent phenomena in two-dimensional (2D) materials has sparked substantial research efforts in the materials community. A significant experimental challenge for this field is exerting atomistic control over the structure and composition of the constituent 2D layers and understanding how the interactions between layers drives both structure and properties. Segregation of Pb to the surface of three bilayer thick PbSe-SnSe alloy layers was discovered within [(PbxSn1-xSe)1+δ]n(TiSe2)1 heterostructures using electron microscopy. We demonstrate that this segregation is thermodynamically favored to occur when PbxSn1-xSe layers are interdigitated with TiSe2 monolayers. Density-functional theory (DFT) calculations indicate that the observed segregation depends on what is adjacent to the PbxSn1-xSe layers. The interplay between interface and volume free energies controls both the structure and composition of the constituent layers, which can be tuned using layer thickness.

The high-bias and breakdown behavior of suspended mono- and few-layer WS2 was explored by in situ aberration-corrected transmission electron microscopy. The suspended WS2 devices were found to undergo irreversible breakdown at sufficiently high biases due to vaporization of the WS2. Simultaneous to the removal of WS2 was the accompanying formation of few-layer graphene decorated with W and WS2 nanoparticles, with the carbon source attributed to organic residues present on the WS2 surface. The breakdown of few-layer WS2 resulted in the formation of faceted S-depleted WS2 tendrils along the vaporization boundary, which were found to exhibit lattice contraction indicative of S depletion, alongside pure W phases incorporated into the structure, with the interfaces imaged at atomic resolution. The combination of observing the graphitization of the amorphous carbon surface residue, W nanoparticles, and S-depleted WS2 phases following the high-bias WS2 disintegration all indicate a thermal Joule heating breakdown mechanism over an avalanche process, with WS2 destruction promoted by preferential S emission. The observation of graphene formation and the role the thin amorphous carbon layer has in the prebreakdown behavior of the device demonstrate the importance of employing encapsulated heterostructure device architectures that exclude residues.

A Keggin-type polyoxometalate (H3PW12O40) was incorporated into a mesoporous Zr-based MOF (NU-1000) via an impregnation method in aqueous media, resulting in the hybrid material, PW12@NU-1000. The POM@MOF composite was characterized by a suite of physical methods, indicating the retention of crystallinity and high porosity of the parent MOF. The hybrid material was also stable to leaching in aqueous media at varying pH. Finally, the material was tested as a heterogeneous catalyst for the oxidation of 2-chloroethyl ethyl sulfide using hydrogen peroxide as the oxidant. PW12@NU-1000 was shown to have a higher catalytic activity than either of the individual constituents alone.

Colloidal processes such as nucleation, growth, ripening, and dissolution are fundamental to the synthesis and application of engineered nanoparticles, as well as numerous natural systems. In nanocolloids consisting of a dispersion of nanoparticles in solution, colloidal stability is influenced by factors including the particle surface facet and capping layer, and local temperature, chemistry, and acidity. In this paper, we investigate colloidal stability through the real-time manipulation of nanoparticles using in situ liquid cell Scanning Transmission Electron Microscopy (STEM). In a distribution of uniform iron oxide nanoparticles, we use the electron beam to precisely control the local chemistry of the solution and observe the critical role that surface chemistry plays in nanoparticle stability. By functionalizing the nanoparticle surfaces with charged amino acids and peptides, stability can be tuned to promote dissolution, growth, or agglomeration, either permanently or reversibly. STEM imaging is used to quantify kinetics of individual nanoparticles subject to local variations in chemistry. These measurements of dissolution and growth rates of iron oxide nanoparticles provide insights into nanoparticle stability relevant to synthesis and functionalization for biomedical applications.

We systematically unravel the mechanism by which sodium ion reacts electrochemically with ionically layered BiOCl nanosheets. Solution-processed BiOCl nanosheets were cycled using slow scan cyclic ...

© 2018 Author(s). Magnetic properties arising at interfaces of perovskite oxides such as La 0.7 Sr 0.3 CoO 3 (LSCO) and La 0.7 Sr 0.3 MnO 3 (LSMO) depend sensitively on the fine details of their structural properties. In this work, we use high-resolution transmission electron microscopy and spectroscopy to examine the structural and electronic phenomena at the interfaces in two LSCO/LSMO bilayers with reversed growth order. Two different strain mechanisms are at work in these films: compressive or tensile epitaxial strain, and distortion of the octahedral tilt pattern to maintain a network of corner-sharing octahedra. While the epitaxial strain is constant regardless of the growth order, the modification of the octahedral tilt pattern depends on whether the film is grown directly on the substrate or as the second sublayer. As a consequence, exchange spring behavior is observed only when the LSCO sublayer is grown first. The different mechanisms of strain accommodation within the oxygen octahedra network in each material proved to be of critical importance in determining the interfacial structure and thus magnetic and electronic properties of the bilayers.

Within the field of thermoelectric materials for energy conversion magnesium silicide, Mg2Si, is an outstanding candidate due to its low density, abundant constituents and low toxicity. However electronic and thermal tuning of the material is a required necessity to improve its Figure of Merit, zT. Doping of Yb via reactive YbH2 into the structure is performed with the goal of reducing the thermal conductivity. Hydrogen is released as a by-product at high temperatures allowing for facile incorporation of Yb into the structure. We report on the properties of Yb- and Bi-doped Mg2Si prepared with MgH2 and YbH2 with the focus on the synthetic conditions, and samples’ microstructure, investigated by various electron microscopy techniques. Yb is found in the form of both Yb3Si5 inclusions and Yb dopant segregated at the grain boundary substituting for Mg. The addition of 1 at% Yb concentration reduced the thermal conductivity, providing a value of 30 mW/cm K at 800 K. In order to adjust carrier concentration, the sample is additionally doped with Bi. The impact of the microstructure on the transport properties of the obtained material is studied. Idealy, the reduction of the thermal conductivity is achieved by doping with Yb and the electronic transport is adjusted by doping with Bi. Large grain microstructure facilitates the electronic transport. However, the synthetic conditions that provide the optimized microstructure for electrical transport do not facilitate the additional Yb dopant incorporation. Therefore, the Yb and Bi containing sample with the optimized microstructure provides a zT=0.46 at 800 K.

Mg batteries have potential advantages in terms of safety, cost, and reliability over existing battery technologies, but their practical implementations are hindered by the lack of amenable high-voltage cathode materials. The development of cathode materials is complicated by limited understandings of the unique divalent Mg2+ ion electrochemistry and the interaction/transportation of Mg2+ ions with host materials. Here, it is shown that highly dispersed vanadium oxide (V2O5) nanoclusters supported on porous carbon frameworks are able to react with Mg2+ ions reversibly in electrolytes that are compatible with Mg metal, and exhibit high capacities and good reaction kinetics. They are able to deliver initial capacities exceeding 300 mAh g−1 at 40 mA g−1 in the voltage window of 0.5 to 2.8 V. The combined electron microscope, spectroscopy, and electrochemistry characterizations suggest a surface-controlled pseudocapacitive electrochemical reaction, and may be best described as a molecular energy storage mechanism. This work can provide a new approach of using the molecular mechanism for pseudocapacitive storage of Mg2+ for Mg batteries cathode materials.

Amorphous precursor phases have been observed in many crystallization processes in aqueous solution, yet their growth kinetics are not fully understood because of their often transient and unstable nature. In this work, we try to close this knowledge gap by employing liquid-phase scanning transmission electron microscopy (LPSTEM) to study the growth kinetics using amorphous cobalt carbonate (CoCO3) as a model system. Using simultaneous acquisition of bright-field and annular dark-field LPSTEM images, we observe that the volume of the amorphous CoCO3 nanoparticles grows linearly with time. By quantifying and extrapolating electron beam effects to zero dose, the growth rate at native solution conditions is obtained. From the observed linear volume growth and the observation of 10 nm-sized nanoparticles by cryotransmission electron microscopy (cryoTEM), we conclude that growth of amorphous CoCO3 nanoparticles proceeds through assembly of the 10 nm primary particles. Our observations not only provide unique insights into the nanoscale growth kinetics of an amorphous phase in aqueous solution that may open the way to improved synthesis protocols of the Co catalyst for Fischer-Tropsch synthesis. ©

Polyoxometalates (POM) have been deposited onto carbon nanotube (CNT) electrodes using benchtop ion soft landing (SL) enabled by a vortex-confined electrohydrodynamic desolvation process. The device is based on the dry ion localization and locomotion (DRILL) mass spectrometry interface of Fedorov and co-workers. By adding electrospray emitters, heating the desolvation gas, and operating at high gas flow rates, it is possible to obtain stable ion currents up to -15 nA that are ideal for deposition. Coupled with ambient ion optics, this interface enables desolvated ions to be delivered to surfaces while excluding solvent and counterions. Electron microscopy of surfaces prepared using the device reveal discrete POM and no aggregation that degrades electrode performance. Characterization of POM-coated CNT electrodes in a supercapacitor showed an energy storage capacity similar to that achieved with SL in vacuum. For solutions that produce primarily a single ion by electrospray ionization, benchtop SL offers a simpler and less costly approach for surface modification with applications in catalysis, energy storage, and beyond.

We demonstrate that silanization can control the adhesion of nanostructures to the SiN windows compatible with liquid-cell transmission electron microscopy (LC-TEM). Formation of an (3-aminopropyl)triethoxysilane (APTES) self-assembled monolayer on a SiN window, producing a surface decorated with amino groups, permits strong adhesion of Au nanoparticles to the window. Many of these nanoparticles remain static, undergoing minimal translation or rotation during LC-TEM up to high electron beam current densities due to the strong interaction between the APTES amino group and Au. We then use this technique to perform a direct comparative LC-TEM study on the behavior of ligand and nonligand-coated Au nanoparticles in a Au growth solution. While the ligand coated nanoparticles remain consistent even under high electron beam current densities, the naked nanoparticles acted as sites for secondary Au nucleation. These nucleated particles decorated the parent nanoparticle surface, forming consecutive monolayer assemblies of ∼2 nm diameter nanoparticles, which sinter into the parent particle when the electron beam was shut off. This method for facile immobilization of nanostructures for LC-TEM study will permit more sophisticated and controlled in situ experiments into the properties of solid-liquid interfaces in the future.

© the Owner Societies 2016. In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here we report that the ionic conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film-substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary "design" as an attractive method to obtain highly conductive solid electrolyte thin films.

This paper demonstrates intermetallic compounds SnSb are highly active materials for reversibly hosting Mg ions. Compared with monometallic Sn and Sb, SnSb alloy exhibited exceptionally high reversible capacity (420 mAh/g), excellent rate capability and good cyclic stability. Mg insertion into pristine SnSb involves an activation process to complete, which induces particle breakdown and results in phase segregation to Sn-rich and Sb-rich phases. Both experimental analysis and DFT simulation suggest that the Sn-rich phase is particularly active and provides most of the capacity whereas the Sb-rich phase is not as active, and the interface between these two phases play a key role in promoting the formation and stabilization of the cubic Sn phase that is more favorable for fast and reversible Mg insertion. We further show that activated SnSb alloy has good compatibility with simple Mg electrolytes. Overall, this work could provide new approaches for designing materials capable of reversible Mg ion insertion and new opportunities for understanding Mg electrochemistry.

Observations are presented, obtained by in situ straining and conventional TEM, of a transformation mechanism by coordinated secondary twinning predicted by Mullner and King. The material studied is the martensitic phase of a non-modulated Ni–Mn–Ga alloy, which exhibits a microstructure comprising domains of lamellar matrix/twin composites. Straining these specimens induced lamellar domains to transform into their conjugate counterparts. In this process, secondary twinning generates a change of misorientation between the matrix and twin lamellae of the initial domain by nearly 23°. The orientation evolves over a region behind the transformation front about 100 nm in extent.

MgAlOx mixed oxides were employed as supports for potassium-based lean NOx traps (LNTs) targeted for high-temperature applications. Effects of support compositions, K/Pt loadings, thermal aging, and catalyst regeneration on NOx storage capacity were systematically investigated. The catalysts were characterized by XRD, NOx-TPD, TEM, STEM-HAADF, and in situ XAFS. The results indicate that MgAlOx mixed oxides have significant advantages over conventional γ-Al2O3 supports for LNT catalysts, in terms of high-temperature NOx trapping capacity and thermal stability. First, as a basic support, MgAlOx stabilizes stored nitrates (in the form of KNO3) to much higher temperatures in comparison to mildly acidic γ-Al2O3. Second, MgAlOx minimizes Pt sintering during thermal aging, which is not possible for γ-Al2O3 supports. Notably, combined XRD, in situ XAFS, and STEM-HAADF results indicate that Pt species in the thermally aged Pt/MgAlOx samples are finely dispersed in the oxide matrix as isolated atoms. This strong me...

Agglomerative sintering of an atomically dispersed, zeolite Y-supported catalyst, Ir1/zeolite Y, formed initially from the well-characterized precatalyst [Ir(C2H4)2]/zeolite Y and in the presence of liquid-phase reactants, was monitored over three cycles of 3800 turnovers (TTOs) of cyclohexene hydrogenation at 72 °C. The catalyst evolved and sintered during each cycle, even at the relatively mild temperature of 72 °C in the presence of the cyclohexene plus H2 reactants and cyclohexane solvent. Post each of the three cycles of catalysis, the resultant sintered catalyst was characterized by extended X-ray absorption fine structure spectroscopy and atomic-resolution high-angle annular dark-field scanning transmission electron microscopy. The results show that higher-nuclearity iridium species, Irn, are formed during each successive cycle. The progression from the starting mononuclear precursor, Ir1, is first to Ir∼4–6; then, on average, Ir∼40; and finally, on average, Ir∼70, the latter more accurately descri...

The compound LaCa2Fe3O8+y, also known as the Grenier phase, is known to undergo an order-disorder transformation (ODT) at high temperatures. Oxidation has been observed when the compound is cooled in air after the ODT. In this study, we have synthesized the Grenier compound in air using traditional solid state reactions and investigated the structure and composition before and after the ODT. Thermal analysis showed that the material undergoes an order-disorder transformation in both oxygen and argon atmospheres with dynamic, temperature dependent, oxidation upon cooling. Results from scanning transmission electron microscopy (STEM) suggest that the Grenier phase has preferential segregation of Ca and La on the two crystallographic A-sites before the ODT, but a random distribution above the ODT temperature. Furthermore, STEM images suggest the possibility that oxygen excess may exist in La-rich regions within microdomains rather than at microdomain boundaries.

We report tip-enhanced Raman imaging experiments in which information on sample topography and local electric fields is simultaneously obtained using an all-optical detection scheme. We demonstrate how a Raman-active 4,4'-dimercaptostilbene (DMS)-coated gold tip of an atomic force microscope can be used to simultaneously map the topography and image the electric fields localized at nanometric (20 and 5 nm wide) slits lithographically etched in silver, all using optical signals. Bimodal imaging is feasible by virtue of the frequency-resolved optical response of the functionalized metal probe. Namely, the probe position-dependent signals can be subdivided into two components. The first is a 500-2250 cm(-1) Raman-shifted signal, characteristic of the tip-bound DMS molecules. The molecules report on topography through the intensity contrast observed as the tip scans across the nanoscale features. The variation in molecular Raman activity arises from the absence/formation of a plasmonic junction between the scanning probe and patterned silver surface, which translates into dimmed/enhanced Raman signatures of DMS. Using these molecular signals, we demonstrate that sub-15 nm spatial resolution is attainable using a 30 nm DMS-coated gold tip. The second response consists of two correlated sub-500 cm(-1) signals arising from mirror-like reflections of (i) the incident laser field and (ii) the Raman scattered response of an underlying glass support (at 100-500 cm(-1)) off the gold tip. We show that both the reflected low-wavenumber signals trace the local electric fields in the vicinity of the nanometric slits.

Magnesium is of great interest as a replacement for lithium in next-generation ion-transfer batteries but Mg-metal anodes currently face critical challenges related to the formation of passivating layers during Mg-plating/stripping and anode-electrolyte-cathode incompatibilities. Alternative anode materials have the potential to greatly extend the spectrum of suitable electrolyte chemistries but must be systematically tailored for effective Mg(2+) storage. Using analytical (scanning) transmission electron microscopy ((S)TEM) and ab initio modeling, we have investigated Mg(2+) insertion and extraction mechanisms and transformation processes in β-SnSb nanoparticles (NPs), a promising Mg-alloying anode material. During the first several charge-discharge cycles (conditioning), the β-SnSb particles irreversibly transform into a porous network of pure-Sn and Sb-rich subparticles, as Mg ions replace Sn atoms in the SnSb lattice. After electrochemical conditioning, small Sn particles/grains (33 ± 20 nm) exhibit highly reversible Mg-storage, while the Sb-rich domains suffer substantial Mg trapping and contribute little to the system performance. This result strongly indicates that pure Sn can act as a high-capacity Mg-insertion anode as theoretically predicted, but that its performance is strongly size-dependent, and stable nanoscale Sn morphologies (40 nm) are needed for superior, reversible Mg-storage and fast system kinetics.

Strain engineering of epitaxial ferroelectrics has emerged as a powerful method to tailor the electromechanical response of these materials, although the effect of strain at the atomic scale and the interplay between lattice displacements and electronic structure changes are not yet fully understood. Here, using a combination of scanning transmission electron microscopy (STEM) and density functional theory (DFT), we systematically probe the role of epitaxial strain in mixed phase bismuth ferrite thin films. Electron energy loss O K and Fe L2,3 edge spectra acquired across the rhombohedral (R)–tetragonal (T) phase boundary reveal progressive, and systematic, changes in electronic structure going from one phase to the other. The comparison of the acquired spectra with theoretical simulations using DFT suggests a breakage in the structural symmetry across the boundary due to the simultaneous presence of increasing epitaxial strain and off-axial symmetry in the T phase. This implies that the imposed epitaxial strain plays a significant role in not only changing the crystal-field geometry, but also the bonding environment surrounding the central iron cation at the interface thus providing new insights and a possible link to understand how the imposed strain could perturb magnetic ordering in the T phase BFO.

An improved understanding of grain growth kinetics in nanocrystalline materials, and in metals and alloys in general, is of continuing interest to the scientific community. In this study, Mg-Al thin films containing ~10 wt pct Al and with 14.5 nm average grain size were produced by magnetron sputtering and subjected to heat treatments. The grain growth evolution in the early stages of heat treatment at 423 K, 473 K, and 573 K (150 °C, 200 °C, and 300 °C) was observed with transmission electron microscopy and analyzed based upon the classical equation developed by Burke and Turnbull. The grain growth exponent was found to be 7 ± 2 and the activation energy for grain growth was 31.1 ± 13.4 kJ/mol, the latter being significantly lower than in bulk Mg-Al alloys. The observed grain growth kinetics are explained by the Al supersaturation in the matrix and the pinning effects of the rapidly forming beta precipitates and possibly shallow grain boundary grooves. The low activation energy is attributed to the rapid surface diffusion which is dominant in thin film systems.

The long-term operation of Li–O2 batteries under full discharge/charge conditions is investigated in a glyme-based electrolyte. The formation of stable interfacial layer on the electrode surface during the initial cycling stabilizes reaction products at subsequent cycling stages as demonstrated by quantitative analyses of the discharge products and the gases released during charging. There is a quick switch from the predominant formation of Li2O2 to the predominant formation of side products during the first few cycles. However, after the formation of the stable interfacial layer, the yield of Li2O2 in the reaction products is stabilized at about 33–40%. Extended cycling under full discharge/charge conditions is achievable upon selection of appropriate electrode materials (carbon source and catalyst) and cycling protocol. Further investigation on the interfacial layer, which in situ forms on air electrode, may increase the long-term yield of Li2O2 during the cycling and enable highly reversible Li–O2 batt...

Dealuminated zeolite HY was used to support Ir(CO)_2 complexes formed from Ir(CO)_2(C_5H_7O_2). Infrared and X-ray absorption spectra and atomic resolution electron microscopy images identify these complexes, and the images and ^(27)Al NMR spectra identify impurity amorphous regions in the zeolite where the iridium is more susceptible to aggregation than in the crystalline regions. The results indicate the value of electron microscopy in characterizing the amorphous impurity regions of zeolites and a significant stability limitation of metals in these regions of zeolite catalyst supports.

The microstructure of a Ni–Mn–Ga alloy in the martensitic phase was investigated using transmission electron microscopy. Inter-variant twin boundaries were observed separating non-modulated tetragonal martensite variants. In addition, intra-variant boundary structures, referred to here as “conjugation boundaries”, were also observed. We propose that conjugation boundaries originate at the transformation interface between austenite and a nascent martensite variant. In the alloy studied, deformation twinning was observed, consistent with being the mode of lattice-invariant deformation, and this can occur on either of two crystallographically equivalent conjugate { 1 0 1 } 〈 1 0 1 ¯ 〉 twinning systems: conjugation boundaries separate regions within a single variant in which the active modes were distinct. The defect structure of conjugation boundaries and the low-angle of misorientation across them are revealed in detail using high-resolution microscopy. We anticipate that the mobility of such boundaries is lower than that of inter-variant boundaries, and is therefore likely to significantly affect the kinetics of deformation in the martensitic phase.

Subsampled image acquisition followed by image inpainting in a scanning transmission electron microscope is a novel approach to control dose and increase the image frame rate during experiments, thereby allowing independent control of the spatial and temporal dose envelope during image acquisition. Here, subsampled imaging is shown to permit precise in situ observations of the fundamental kinetic processes behind nucleation and growth of silver (Ag) nanoparticles from an aqueous solution. At high sampling-levels, nanoparticles can be observed with morphologies that are consistent with strong interface interactions, i.e., rafts and pillars, whereas at low sampling-levels, the particles exhibit regular spherical morphologies. The relative numbers of rafts/pillars and regular nanoparticles, their sizes, and their incubation times can be attributed to local changes in the molar concentration of the Ag ions in the aqueous solution; higher sampling-levels significantly increase the reactants in the vicinity of the window, leading to rapid supersaturation and the precipitation on the window surface. These precisely controlled kinetics highlight subsampled imaging as a method by which the driving force for nucleation and growth (i.e., the electron beam) can be disentangled from the spatial/temporal resolution of the observation in all in situ experiments, providing a pathway to identify and quantify the importance of individual kinetic factors behind nucleation and growth in a wide variety of complex materials systems and architectures. The development of Compressive sensing for EM applications was supported by the Chemical Imaging Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U. S. Department of Energy (DOE) under Contract No. DE-AC05-76RL01830. A portion of the research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at PNNL.