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Images and spectra obtained from aberration corrected scanning transmission electron microscopes (STEM) are now used routinely to quantify the morphology, structure, composition, chemistry, bonding, and optical/electronic properties of nanostructures, interfaces, and defects in many materials/biological systems. However, obtaining quantitative and reproducible atomic resolution observations from some experiments is actually harder with these ground-breaking instrumental capabilities, as the increase in beam current from using the correctors brings with it the potential for electron beam modification of the specimen during image acquisition. This beam effect is even more acute for in situ STEM observations, where the desired outcome being investigated is a result of a series of complicated transients, all of which can be modified in unknown ways by the electron beam. The aim in developing and applying new methods in STEM is, therefore, to focus on more efficient use of the dose that is supplied to the sample and to extract the most information from each image (or set of images). For STEM (and for that matter, all electron/ion/photon scanning systems), one way to achieve this is by sub-sampling the image and using Inpainting algorithms to reconstruct it. By separating final image quality from overall dose in this way and manipulating the dose distribution to be best for the stability of the sample, images can be acquired both faster and with less beam effects. In this paper, the methodology behind sub-sampling and Inpainting is described, and the potential for Inpainting to be applied to novel real time dynamic experiments will be discussed.

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.

Conjugated polymers have received significant attention as photocatalysts. However, photocatalytic oxygen evolution has only been reported for a few polymers so far. Here, we present a bipyridine based covalent triazine-based framework containing metal coordination sites (Bpy-CTF). The material is highly active for sacrificial photocatalytic oxygen evolution with a rate of 322 μmol g−1 h−1 under visible light illumination (≥420 nm) after post-synthetic cobalt coordination. An analogous photocatalyst containing biphenyl was found to be less active as it is not able to coordinate cobalt. Transient absorption spectroscopy studies showed that the cobalt coordinated in the bipyridine units of Bpy-CTF promotes charge separation and transfer, thus increasing water oxidation activity. The study demonstrates the growing potential of polymer photocatalysts for oxygen evolution by structural engineering and post-synthetic metalation.

The large scale recycling of lithium ion batteries (LIBs) is essential to satisfy global demands for the raw materials required to implement this technology as part of a clean energy strategy. However, despite what is rapidly becoming a critical need, an efficient and sustainable recycling process for LIBs has yet to be developed. Biological reactions occur with great selectivity under mild conditions, offering new avenues for the implementation of more environmentally sustainable processes. Here, we demonstrate a sequential process employing two bacterial species to recover Mn, Co and Ni, from vehicular LIBs through the biosynthesis of metallic nanoparticles, whilst Li remains within the leachate. Moreover the feasibility of Mn recovery from polymetallic solutions was demonstrated at semi-pilot scale in a 30 L bioreactor. Additionally, to provide insight into the biological process occurring, we investigated selectivity between Co and Ni using proteomics to identify the biological response and confirm the potential of a bio-based method to separate these two essential metals. Our approach determines the principles and first steps of a practical bio-separation and recovery system, underlining the relevance of harnessing biological specificity for recycling and up-cycling critical materials.

Polymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large‐scale hydrogen energy production. Here we show that the palladium/iridium oxide‐loaded homopolymer of dibenzo[b, d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co‐catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co‐catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co‐catalyst.

Scanning transmission electron microscopy (STEM) provides structural analysis with sub-angstrom resolution. But the pixel-by-pixel scanning process is a limiting factor in acquiring high-speed data. Different strategies have been implemented to increase scanning speeds while at the same time minimizing beam damage via optimizing the scanning strategy. Here, we achieve the highest possible scanning speed by eliminating the image acquisition dead time induced by the beam flyback time combined with reducing the amount of scanning pixels via sparse imaging. A calibration procedure was developed to compensate for the hysteresis of the magnetic scan coils. A combination of sparse and serpentine scanning routines was tested for a crystalline thin film, gold nanoparticles, and in an in-situ liquid phase STEM experiment. Frame rates of 92, 23 and 5.8 s-1 were achieved for images of a width of 128, 256, and 512 pixels, respectively. The methods described here can be applied to single-particle tracking and analysis of radiation sensitive materials.

Electrochemically active covalent organic frameworks (COFs) are promising electrode materials for Li-ion batteries. However, improving the specific capacities of COF-based electrodes requires materials with increased conductivity and a higher concentration of redox-active groups. Here, we designed a series of pyrene-4,5,9,10-tetraone COF (PT-COF) and carbon nanotube (CNT) composites (denoted as PT-COFX, where

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...

Recently it has been shown that precise dose control and an increase in the overall acquisition speed of atomic resolution scanning transmission electron microscope (STEM) images can be achieved by acquiring only a small fraction of the pixels in the image experimentally and then reconstructing the full image using an inpainting algorithm. In this paper, we apply the same inpainting approach (a form of compressed sensing) to simulated, sub-sampled atomic resolution STEM images. We find that it is possible to significantly sub-sample the area that is simulated, the number of g-vectors contributing the image, and the number of frozen phonon configurations contributing to the final image while still producing an acceptable fit to a fully sampled simulation. Here we discuss the parameters that we use and how the resulting simulations can be quantifiably compared to the full simulations. As with any Compressed Sensing methodology, care must be taken to ensure that isolated events are not excluded from the process, but the observed increase in simulation speed provides significant opportunities for real time simulations, image classification and analytics to be performed as a supplement to experiments on a microscope to be developed in the future., Comment: 20 pages (includes 3 supplementary pages), 15 figures (includes 5 supplementary figures), submitted to Ultramicroscopy

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.

The synthesis of three-dimensional (3D) covalent organic frameworks (COFs) requires high-connectivity polyhedral building blocks or the controlled alignment of building blocks. Here, we use the latter strategy to assemble square-planar cobalt(II) phthalocyanine (PcCo) units into the nbo topology by using tetrahedral spiroborate (SPB) linkages that were chosen to provide the necessary 90° dihedral angles between neighboring PcCo units. This yields a porous 3D COF, SPB-COF-DBA, with a noninterpenetrated nbo topology. SPB-COF-DBA shows high crystallinity and long-range order, with 11 resolved diffraction peaks in the experimental powder X-ray diffraction (PXRD) pattern. This well-ordered crystal lattice can also be imaged by using high-resolution transmission electron microscopy (HR-TEM). SPB-COF-DBA has cubic pores and exhibits permanent porosity with a Brunauer-Emmett-Teller (BET) surface area of 1726 m2 g-1.

When high-energy electrons from a scanning transmission electron microscope (STEM) are incident on a liquid, the vast majority of the chemical reactions that are observed are induced by the radiolysis breakdown of the liquid molecules. In the study of liquids, the radiolysis products of pure water are well known, and their rate of formation for a given flux of high-energy electrons has been studied intensively over the last few years for uniform TEM illumination. In this paper, we demonstrate that the temporal and spatial distribution of the electron illumination can significantly affect the final density of radiolysis products in water and even change the type of reaction taking place. We simulate the complex array of possible spatial/temporal distributions of electrons that are accessible experimentally by controlling the size, the scan rate and the hopping distance of the electron probe in STEM mode and then compare the results to the uniformly illuminated TEM mode of imaging. By distributing the electron dose both spatially and temporally in the STEM through a randomised “spot-scan” mode of imaging, the diffusion overlap of the radiolysis products can be reduced, and the resulting reactions can be more readily controlled. This control allows the resolution of the images to be separated from the speed of the induced reaction (which is based on beam current alone) and this facet of the experiment will allow a wide range of chemical reactions to be uniquely tailored and observed in all liquid cell STEM experiments.

Making efficient and timely inferences about data generated by real-time systems is challenging, as they often consist of high-volume, high-velocity data streams. In particular, when a user interac...

Sub-sampling during image acquisition in scanning transmission electron microscopy (STEM) has been shown to provide a means to increase the overall speed of acquisition while at the same time providing an efficient means to control the dose, dose rate and dose overlap delivered to the sample. In this paper, we discuss specifically the parameters used to reconstruct sub-sampled images and highlight their effect on inpainting using the beta-process factor analysis (BPFA) methodology. The selection of the main control parameters can have a significant effect on the resolution, precision and sensitivity of the final inpainted images, and here we demonstrate a method by which these parameters can be optimised for any image in STEM. As part of this work, we also provide a link to open source code and a tutorial on its use, whereby these parameters can be tested for any datasets. When coupled with the hardware necessary to rapidly sub-sample images in STEM, this approach can have significant implications for imaging beam sensitive materials and dynamic processes.

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...