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The high carbon intensity of present-day ethylene glycol (EG) production motivates interest in electrifying ethylene oxidation. Noting poor kinetics in prior reports of the organic electrooxidation of small hydrocarbons, we explored the design of mediators that activate and simultaneously stabilize light alkenes. A ruthenium-substituted polyoxometalate (Ru-POM, {Si[Ru(H 2 O)W 11 O 39 ]} 5- ) achieves 82% faradaic efficiency in EG production at 100 mA/cm 2 under ambient conditions. Via the union of in situ spectroscopic techniques, electrochemical studies, and density functional theory calculations, we find evidence of a two-step oxidation mechanism: Ru-POM first undergoes electrochemical oxidation to the high valent state, activating ethylene via partial oxidation and forming an intermediate complex; this intermediate complex then migrates to the anode where it undergoes further oxidation to produce EG. The Ru-POM-mediated electrocatalytic system reduces the projected energy consumption required in EG production, requiring 9 GJ per ton of EG (and accompanied by 0.04 ton H 2 coproduction), compared to 20-30 GJ/ton in typical prior processes.

Introducing nanotwins in thermoelectric materials represents a promising approach to achieving such a synergistic combination of thermoelectric properties and mechanical properties. By increasing configurational entropy, a sharply reduced stacking fault energy in a new nanotwinned high-entropy semiconductor AgMnGePbSbTe 5 is reached. Dense coherent nanotwin boundaries in this system provide an efficient phonon scattering barrier, leading to a high figure of merit ZT of ≈2.46 at 750 K and a high average ZT of ≈1.54 (300-823 K) with the presence of Ag 2 Te nanoprecipitate in the sample. More importantly, owing to the dislocation pinning caused by coherent nanotwin boundaries and the chemical short-range disorder caused by the high configurational entropy effect, AgMnGePbSbTe 5 also exhibits robust mechanical properties, with flexural strength of 82 MPa and Vickers hardness of 210 H V ., (© 2024 Wiley‐VCH GmbH.)

Graphite is a commonly used raw material across many industries and the demand for high-quality graphite has been increasing in recent years, especially as a primary component for lithium-ion batteries. However, graphite production is currently limited by production shortages, uneven geographical distribution, and significant environmental impacts incurred from conventional processing. Here, an efficient method of synthesizing biomass-derived graphite from biochar is presented as a sustainable alternative to natural and synthetic graphite. The resulting bio-graphite equals or exceeds quantitative quality metrics of spheroidized natural graphite, achieving a Raman I D /I G ratio of 0.051 and crystallite size parallel to the graphene layers (L a ) of 2.08 µm. This bio-graphite is directly applied as a raw input to liquid-phase exfoliation of graphene for the scalable production of conductive inks. The spin-coated films from the bio-graphene ink exhibit the highest conductivity among all biomass-derived graphene or carbon materials, reaching 3.58 ± 0.16 × 10 4 S m -1 . Life cycle assessment demonstrates that this bio-graphite requires less fossil fuel and produces reduced greenhouse gas emissions compared to incumbent methods for natural, synthesized, and other bio-derived graphitic materials. This work thus offers a sustainable, locally adaptable solution for producing state-of-the-art graphite that is suitable for bio-graphene and other high-value products., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Palladium (Pd) catalysts have been extensively studied for the direct synthesis of H 2 O through the hydrogen oxidation reaction at ambient conditions. This heterogeneous catalytic reaction not only holds considerable practical significance but also serves as a classical model for investigating fundamental mechanisms, including adsorption and reactions between adsorbates. Nonetheless, the governing mechanisms and kinetics of its intermediate reaction stages under varying gas conditions remain elusive. This is attributed to the intricate interplay between adsorption, atomic diffusion, and concurrent phase transformation of catalyst. Herein, the Pd-catalyzed, water-forming hydrogen oxidation is studied in situ, to investigate intermediate reaction stages via gas cell transmission electron microscopy. The dynamic behaviors of water generation, associated with reversible palladium hydride formation, are captured in real time with a nanoscale spatial resolution. Our findings suggest that the hydrogen oxidation rate catalyzed by Pd is significantly affected by the sequence in which gases are introduced. Through direct evidence of electron diffraction and density functional theory calculation, we demonstrate that the hydrogen oxidation rate is limited by precursors' adsorption. These nanoscale insights help identify the optimal reaction conditions for Pd-catalyzed hydrogen oxidation, which has substantial implications for water production technologies. The developed understanding also advocates a broader exploration of analogous mechanisms in other metal-catalyzed reactions., Competing Interests: Competing interests statement:The authors declare no competing interest.

The growth of layered 2D compounds is a key ingredient in finding new phenomena in quantum materials, optoelectronics, and energy conversion. Here, we report SnP 2 Se 6 , a van der Waals chiral ( R 3 space group) semiconductor with an indirect bandgap of 1.36 to 1.41 electron volts. Exfoliated SnP 2 Se 6 flakes are integrated into high-performance field-effect transistors with electron mobilities >100 cm 2 /Vs and on/off ratios >10 6 at room temperature. Upon excitation at a wavelength of 515.6 nanometer, SnP 2 Se 6 phototransistors show high gain (>4 × 10 4 ) at low intensity (≈10 -6 W/cm 2 ) and fast photoresponse (< 5 microsecond) with concurrent gain of ≈52.9 at high intensity (≈56.6 mW/cm 2 ) at a gate voltage of 60 V across 300-nm-thick SiO 2 dielectric layer. The combination of high carrier mobility and the non-centrosymmetric crystal structure results in a strong intrinsic bulk photovoltaic effect; under local excitation at normal incidence at 532 nm, short circuit currents exceed 8 mA/cm 2 at 20.6 W/cm 2 .

Lithium-ion batteries are the leading energy storage technology for portable electronics and vehicle electrification. However, demands for enhanced energy density, safety, and scalability necessitate solid-state alternatives to traditional liquid electrolytes. Moreover, the rapidly increasing utilization of lithium-ion batteries further requires that next-generation electrolytes are derived from earth-abundant raw materials in order to minimize supply chain and environmental concerns. Toward these ends, clay-based nanocomposite electrolytes hold significant promise since they utilize earth-abundant materials that possess superlative mechanical, thermal, and electrochemical stability, which suggests their compatibility with energy-dense lithium metal anodes. Despite these advantages, nanocomposite electrolytes rarely employ kaolinite, the most abundant variety of clay, due to strong interlayer interactions that have historically precluded efficient exfoliation of kaolinite. Overcoming this limitation, here we demonstrate a scalable liquid-phase exfoliation process that produces kaolinite nanoplatelets (KNPs) with high gravimetric surface area, thus enabling the formation of mechanically robust nanocomposites. In particular, KNPs are combined with a succinonitrile (SN) liquid electrolyte to form a nanocomposite gel electrolyte with high room-temperature ionic conductivity (1 mS cm -1 ), stiff storage modulus (>10 MPa), wide electrochemical stability window (4.5 V vs Li/Li + ), and excellent thermal stability (>100 °C). The resulting KNP-SN nanocomposite gel electrolyte is shown to be suitable for high-rate rechargeable lithium metal batteries that employ high-voltage LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) cathodes. While the primary focus here is on solid-state batteries, our strategy for kaolinite liquid-phase exfoliation can serve as a scalable manufacturing platform for a wide variety of other kaolinite-based nanocomposite applications.

Traditionally, materials discovery has been driven more by evidence and intuition than by systematic design. However, the advent of "big data" and an exponential increase in computational power have reshaped the landscape. Today, we use simulations, artificial intelligence (AI), and machine learning (ML) to predict materials characteristics, which dramatically accelerates the discovery of novel materials. For instance, combinatorial megalibraries, where millions of distinct nanoparticles are created on a single chip, have spurred the need for automated characterization tools. This paper presents an ML model specifically developed to perform real-time binary classification of grayscale high-angle annular dark-field images of nanoparticles sourced from these megalibraries. Given the high costs associated with downstream processing errors, a primary requirement for our model was to minimize false positives while maintaining efficacy on unseen images. We elaborate on the computational challenges and our solutions, including managing memory constraints, optimizing training time, and utilizing Neural Architecture Search tools. The final model outperformed our expectations, achieving over 95% precision and a weighted F-score of more than 90% on our test data set. This paper discusses the development, challenges, and successful outcomes of this significant advancement in the application of AI and ML to materials discovery., Competing Interests: Conflict of Interest C.A.M. and C.B.W. have financial interests in Mattiq, Inc., which could potentially benefit from the outcomes of this research. All other authors declare no competing financial interest., (© The Author(s) 2024. Published by Oxford University Press on behalf of the Microscopy Society of America.)

GeSe, an analogue of SnSe, shows promise in exhibiting exceptional thermoelectric performance in the Pnma phase. The constraints on its dopability, however, pose challenges in attaining optimal carrier concentrations and improving ZT values. This study demonstrates a crystal structure evolution strategy for achieving highly doped samples and promising ZT s in GeSe via LiBiTe 2 alloying. A rhombohedral phase ( R 3 m ) can be stabilized in the GeSe-LiBiTe 2 system, further evolving into a cubic ( Fm 3 ̅m ) phase with a rising temperature. The band structures of GeSe-LiBiTe 2 in the rhombohedral and cubic phases feature a similar multiple-valley energy-converged valence band of L and Σ bands. The observed high carrier concentration (∼10 20 cm -3 ) reflects the effective convergence of these bands, enabling a high density-of-states effective mass and an enhanced power factor. Moreover, a very low lattice thermal conductivity of 0.6-0.5 W m -1 K -1 from 300 to 723 K is achieved in 0.9GeSe-0.1LiBiTe 2 , approaching the amorphous limit value. This remarkably low lattice thermal conductivity is related to phonon scattering from point defects, planar vacancies, and ferroelectric instability-induced low-energy Einstein oscillators. Finally, a maximum ZT value of 1.1 to 1.3 at 723 K is obtained, with a high average ZT value of over 0.8 (400-723 K) in 0.9GeSe-0.1LiBiTe 2 samples. This study establishes a viable route for tailoring crystal structures to significantly improve the performance of GeSe-related compounds.

High-entropy semiconductors are now an important class of materials widely investigated for thermoelectric applications. Understanding the impact of chemical and structural heterogeneity on transport properties in these compositionally complex systems is essential for thermoelectric design. In this work, we uncover the polar domain structures in the high-entropy PbGeSnSe 1.5 Te 1.5 system and assess their impact on thermoelectric properties. We found that polar domains induced by crystal symmetry breaking give rise to well-structured alternating strain fields. These fields effectively disrupt phonon propagation and suppress the thermal conductivity. We demonstrate that the polar domain structures can be modulated by tuning crystal symmetry through entropy engineering in PbGeSnAg x Sb x Se 1.5+ x Te 1.5+ x . Incremental increases in the entropy enhance the crystal symmetry of the system, which suppresses domain formation and loses its efficacy in suppressing phonon propagation. As a result, the room-temperature lattice thermal conductivity increases from κ L = 0.63 Wm -1 K -1 ( x = 0) to 0.79 Wm -1 K -1 ( x = 0.10). In the meantime, the increase in crystal symmetry, however, leads to enhanced valley degeneracy and improves the weighted mobility from μ w = 29.6 cm 2 V -1 s -1 ( x = 0) to 35.8 cm 2 V -1 s -1 ( x = 0.10). As such, optimal thermoelectric performance can be achieved through entropy engineering by balancing weighted mobility and lattice thermal conductivity. This work, for the first time, studies the impact of polar domain structures on thermoelectric properties, and the developed understanding of the intricate interplay between crystal symmetry, polar domains, and transport properties, along with the impact of entropy control, provides valuable insights into designing GeTe-based high-entropy thermoelectrics.

Mixed metal oxyhalides are an exciting class of photocatalysts, capable of the sustainable generation of fuels and remediation of pollutants with solar energy. Bismuth oxyhalides of the types Bi 4 MO 8 X (M = Nb and Ta; X = Cl and Br) and Bi 2 AO 4 X (A = most lanthanides; X = Cl, Br, and I) have an electronic structure that imparts photostability, as their valence band maxima (VBM) are composed of O 2p orbitals rather than X n p orbitals that typify many other bismuth oxyhalides. Here, flux-based synthesis of intergrowth Bi 4 NbO 8 Cl-Bi 2 GdO 4 Cl is reported, testing the hypothesis that both intergrowth stoichiometry and M identity serve as levers toward tunable optoelectronic properties. X-ray scattering and atomically resolved electron microscopy verify intergrowth formation. Facile manipulation of the Bi 4 NbO 8 Cl-to-Bi 2 GdO 4 Cl ratio is achieved with the specific ratio influencing both the crystal and electronic structures of the intergrowths. This compositional flexibility and crystal structure engineering can be leveraged for photocatalytic applications, with comparisons to the previously reported Bi 4 TaO 8 Cl-Bi 2 GdO 4 Cl intergrowth revealing how subtle structural and compositional features can impact photocatalytic materials.

Despite global efforts to reduce carbon dioxide (CO 2 ) emissions, continued industrialization threatens to exacerbate climate change. This work investigates methods to capture CO 2 , with a focus on the SIFSIX-3-Ni metal-organic framework (MOF) as a direct air capture (DAC) sorbent. SIFSIX-3-Ni exhibits promising CO 2 adsorption properties but suffers from degradation processes under accelerated aging, which are akin to column regeneration conditions. Herein, we have grown the largest SIFSIX-3-Ni single crystals to date, facilitating single crystal X-ray diffraction analyses that enabled direct observation of the H 2 O and CO 2 dynamics through adsorption and desorption. In addition, a novel space group ( I 4/ mcm ) for the SIFSIX-3-Ni is identified, which provided insights into structural transitions within the framework and elucidated water's role in degrading CO 2 uptake performance as the material ages. In situ X-ray scattering methods revealed long-range and local structural transformations associated with CO 2 adsorption in the framework pores as well as a temperature-dependent desorption mechanism. Pair distribution function analysis revealed a partial decomposition to form nonporous single-layer nanosheets of edge-sharing nickel oxide octahedra upon aging. The formation of these nanosheets is irreversible and reduces the amount of active material for the CO 2 sorption. These findings provide crucial insights for the development of efficient and stable DAC sorbents, effectively reducing greenhouse gases, and suggest avenues for enhancing MOF stability under practical DAC conditions.

Utilization of in situ/operando methods with broad beams and localized probes has accelerated our understanding of fluid-surface interactions in recent decades. The closed-cell microchips based on silicon nitride (SiN x ) are widely used as "nanoscale reactors" inside the high-vacuum electron microscopes. However, the field has been stalled by the high background scattering from encapsulation (typically ~100 nanometers) that severely limits the figures of merit for in situ performance. This adverse effect is particularly notorious for gas cell as the sealing membranes dominate the overall scattering, thereby blurring any meaningful signals and limiting the resolution. Herein, we show that by adopting the back-supporting strategy, encapsulating membrane can be reduced substantially, down to ~10 nanometers while maintaining structural resiliency. The systematic gas cell work demonstrates advantages in figures of merit for hitherto the highest spatial resolution and spectral visibility. Furthermore, this strategy can be broadly adopted into other types of microchips, thus having broader impact beyond the in situ/operando fields.

Platinum (Pt) thin films are useful in applications requiring high-conductivity electrodes with excellent thermal and chemical stability. Ultrasmooth and epitaxial Pt thin films with single-crystalline domains have the added benefit of providing ideal templates for the subsequent growth of heteroepitaxial structures. Here, we grow epitaxial Pt (111) electrodes (ca. 30 nm thick) on sapphire (α-Al 2 O 3 (0001)) substrates with pulsed laser deposition. This versatile technique allows control of the growth process and fabrication of films with carefully tailored parameters. X-ray scattering, atomic-force microscopy, and electron microscopy provide structural characterization of the films. Various gaseous atmospheres and temperatures were explored to achieve epitaxial growth of films with low roughness. A two-step (500 °C/300 °C) growth process was developed, yielding films with improved epitaxy without compromising roughness. The resulting films possess ultrasmooth interfaces (<3 Å) and high electrical conductivity (6.9 × 10 6 S/m). Finally, Pt films were used as current collectors and templates to grow lithium manganese oxide (LiMn 2 O 4 (111)) epitaxial thin films, a cathode material used in Li-ion batteries. Using a solid-state ionogel electrolyte, the films were highly stable when electrochemically cycled in the 3.5-4.3 V vs Li/Li + range.

Coupling plasmonic and functional materials provides a promising way to generate multifunctional structures. However, finding plasmonic nanomaterials and elucidating the roles of various geometric and dielectric configurations are tedious. This work describes a combinatorial approach to rapidly exploring and identifying plasmonic heteronanomaterials. Symmetry-broken noble/non-noble metal particle heterojunctions (~100 nanometers) were synthesized on multiwindow silicon chips with silicon nitride membranes. The metal types and the interface locations were controlled to establish a nanoparticle library, where the particle morphology and scattering color can be rapidly screened. By correlating structural data with near- and far-field single-particle spectroscopy data, we found that certain low-energy plasmonic modes could be supported across the heterointerface, while others are localized. Furthermore, we found a series of triangular heteronanoplates stabilized by epitaxial Moiré superlattices, which show strong plasmonic responses despite largely comprising a lossy metal (~70 atomic %). These architectures can become the basis for multifunctional and cost-effective plasmonic devices.

In a scanning transmission electron microscope (STEM), producing a high-resolution image generally requires an electron beam focused to the smallest point possible. However, the magnetic lenses used to focus the beam are unavoidably imperfect, introducing aberrations that limit resolution. Modern STEMs overcome this by using hardware aberration correctors comprised of many multipole elements, but these devices are complex, expensive, and can be difficult to tune. We demonstrate a design for an electrostatic phase plate that can act as an aberration corrector. The corrector is comprised of annular segments, each of which is an independent two-terminal device that can apply a constant or ramped phase shift to a portion of the electron beam. We show the improvement in image resolution using an electrostatic corrector. Engineering criteria impose that much of the beam within the probe-forming aperture be blocked by support bars, leading to large probe tails for the corrected probe that sample the specimen beyond the central lobe. We also show how this device can be used to create other STEM beam profiles such as vortex beams and probes with a high degree of phase diversity, which improve information transfer in ptychographic reconstructions., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Microscopy Society of America.)

Calcium carbonate (CaCO 3 ), the most abundant biogenic mineral on earth, plays a crucial role in various fields such as hydrosphere, biosphere, and climate regulation. Of the four polymorphs, calcite, aragonite, vaterite, and amorphous CaCO 3 , vaterite is the most enigmatic one due to an ongoing debate regarding its structure that has persisted for nearly a century. In this work, based on systematic transmission electron microscopy characterizations, crystallographic analysis and machine learning aided molecular dynamics simulations with ab initio accuracy, we reveal that vaterite can be regarded as a polytypic structure. The basic phase has a monoclinic lattice possessing pseudohexagonal symmetry. Direct imaging and atomic-scale simulations provide evidence that a single grain of vaterite can contain three orientation variants. Additionally, we find that vaterite undergoes a second-order phase transition with a critical point of ~190 K. These atomic scale insights provide a comprehensive understanding of the structure of vaterite and offer advanced perspectives on the biomineralization process of calcium carbonate., (© 2023. The Author(s).)

A bottleneck in high-throughput nanomaterials discovery is the pace at which new materials can be structurally characterized. Although current machine learning (ML) methods show promise for the automated processing of electron diffraction patterns (DPs), they fail in high-throughput experiments where DPs are collected from crystals with random orientations. Inspired by the human decision-making process, a framework for automated crystal system classification from DPs with arbitrary orientations was developed. A convolutional neural network was trained using evidential deep learning, and the predictive uncertainties were quantified and leveraged to fuse multiview predictions. Using vector map representations of DPs, the framework achieves a testing accuracy of 0.94 in the examples considered, is robust to noise, and retains remarkable accuracy using experimental data. This work highlights the ability of ML to be used to accelerate experimental high-throughput materials data analytics.

The increase in the atmospheric carbon dioxide level is a significant threat to our planet, and therefore the selective removal of CO 2 from the air is a global concern. Metal-organic frameworks (MOFs) are a class of porous materials that have shown exciting potential as adsorbents for CO 2 capture due to their high surface area and tunable properties. Among several implemented technologies, direct air capture (DAC) using MOFs is a promising strategy for achieving climate targets as it has the potential to actively reduce the atmospheric CO 2 concentration to a safer levels. In this study, we investigate the stability and regeneration conditions of N , N '-dimethylethylenediamine (mmen) appended Mg 2 (dobpdc), a MOF with exceptional CO 2 adsorption capacity from atmospheric air. We employed a series of systematic experiments including thermogravimetric analysis (TGA) coupled with Fourier transformed infrared (FTIR) and gas chromatography mass spectrometer (GCMS) (known as TGA-FTIR-GCMS), regeneration cycles at different conditions, control and accelerated aging experiments. We also quantified CO 2 and H 2 O adsorption under humid CO 2 using a combination of data from TGA-GCMS and coulometric Karl-Fischer titration techniques. The quantification of CO 2 and H 2 O adsorption under humid conditions provides vital information for the design of real-world DAC systems. Our results demonstrate the stability and regeneration conditions of mmen appended Mg 2 (dobpdc). It is stable up to 50% relative humidity when the adsorption temperature varies from 25-40 °C and the best regeneration condition can be achieved at 120 °C under dynamic vacuum and at 150 °C under N 2 ., Competing Interests: The authors declare the following competing financial interest(s): O. K. F. has a financial interest in the start-up company NuMat Technologies, which is seeking to commercialize metal–organic frameworks., (This journal is © The Royal Society of Chemistry.)

The alloyed lead/tin (Pb/Sn) halide perovskites have gained significant attention in the development of tandem solar cells and other optoelectronic devices due to their widely tunable absorption edge. To gain a better understanding of the intriguing properties of Pb/Sn perovskites, such as their anomalous bandgap's dependence on stoichiometry, it is important to deepen the understanding of their chemical behavior and local structure. Herein, we investigate a series of two-dimensional Ruddlesden-Popper (RP) and Dion-Jacobson (DJ) phase alloyed Pb/Sn bromide perovskites using butylammonium (BA) and 3-(aminomethyl)pyridinium (3AMPY) as the spacer cations: (BA) 2 (MA) n -1 Pb x Sn n - x Br 3 n +1 ( n = 1-3) and (3AMPY)(MA) n -1 Pb x Sn n - x Br 3 n +1 ( n = 1-3) through a solution-based approach. Our results show that the ratio and site preference of Pb/Sn atoms are influenced by the layer thickness ( n ) and spacer cations (A'), as determined by single-crystal X-ray diffraction. Solid-state 1 H, 119 Sn, and 207 Pb NMR spectroscopy analysis shows that the Pb atoms prefer the outer layers in n = 3 members: (BA) 2 (MA)Pb x Sn n - x Br 10 and (3AMPY)(MA)Pb x Sn n - x Br 10 . Layered 2D DJ alloyed Pb/Sn bromide perovskites (3AMPY)(MA) n -1 Pb x Sn n - x Br 3 n +1 ( n = 1-3) demonstrate much narrower optical band gaps, lower energy PL emission peaks, and longer carrier lifetimes compared to those of RP analogs. Density functional theory calculations suggest that Pb-rich alloys (Pb:Sn ∼4:1) for n = 1 compounds are thermodynamically favored over 50:50 (Pb:Sn ∼1:1) compositions. From grazing-incidence wide-angle X-ray scattering (GIWAXS), we see that films in the RP phase orient parallel to the substrate, whereas for DJ cases, random orientations are observed relative to the substrate.

Spinel-type lithium manganese oxide (LiMn 2 O 4 ) cathodes suffer from severe manganese dissolution in the electrolyte, compromising the cyclic stability of LMO-based Li-ion batteries (LIBs). In addition to causing structural and morphological deterioration to the cathode, dissolved Mn ions can migrate through the electrolyte to deposit on the anode, accelerating capacity fade. Here, we examine single-crystal epitaxial LiMn 2 O 4 (111) thin-films using synchrotron in situ X-ray diffraction and reflectivity to study the structural and interfacial evolution during cycling. Cyclic voltammetry is performed in a wide range (2.5-4.3 V vs Li/Li + ) to promote Mn 3+ formation, which enhances dissolution, for two different electrolyte systems: an imidazolium ionic liquid containing lithium bis-(trifluoromethylsulfonyl)imide (LiTFSI) and a conventional carbonate liquid electrolyte containing lithium hexafluorophosphate (LiPF 6 ). We find exceptional stability in this voltage range for the ionic liquid electrolyte compared to the conventional electrolyte, which is attributed to the absence of Mn dissolution in the ionic liquid. X-ray reflectivity shows a negligible loss of cathode material for the films cycled in the ionic liquid electrolyte, further confirmed by inductively coupled plasma mass spectrometry and transmission electron microscopy. Conversely, a substantial loss of Mn is found when the film is cycled in the conventional electrolyte. These findings show the significant advantages of ionic liquids in suppressing Mn dissolution in LiMn 2 O 4 LIB cathodes.

Nanoparticles with high-index facets are intriguing because such facets can lend the structure useful functionality, including enhanced catalytic performance and wide-ranging optical tunability. Ligand-free solid-state syntheses of high index-facet nanoparticles, through an alloying-dealloying process with foreign volatile metals, are attractive owing to their materials generality and high yields. However, the role of foreign atoms in stabilizing the high-index facets and the dynamic nature of the transformation including the coarsening and facet regulation process are still poorly understood. Herein, the transformation of Pt salts to spherical seeds and then to tetrahexahedra, is studied in situ via gas-cell transmission electron microscopy. The dynamic behaviors of the alloying and dealloying process, which involves the coarsening of nanoparticles and consequent facet regulation stage are captured in the real time with a nanoscale spatial resolution. Based on additional direct evidence obtained using atom probe tomography and density functional theory calculations, the underlying mechanisms of the alloying-dealloying process are uncovered, which will facilitate broader explorations of high-index facet nanoparticle synthesis., (© 2023. The Author(s).)

Material properties strongly depend on the nature and concentration of defects. Characterizing these features may require nano- to atomic-scale resolution to establish structure-property relationships. 4D-STEM, a technique where diffraction patterns are acquired at a grid of points on the sample, provides a versatile method for highlighting defects. Computational analysis of the diffraction patterns with virtual detectors produces images that can map material properties. Here, using multislice simulations, we explore different virtual detectors that can be applied to the diffraction patterns that go beyond the binary response functions that are possible using ordinary STEM detectors. Using graphene and lead titanate as model systems, we investigate the application of virtual detectors to study local order and in particular defects. We find that using a small convergence angle with a rotationally varying detector most efficiently highlights defect signals. With experimental graphene data, we demonstrate the effectiveness of these detectors in characterizing atomic features, including vacancies, as suggested in simulations. Phase and amplitude modification of the electron beam provides another process handle to change image contrast in a 4D-STEM experiment. We demonstrate how tailored electron beams can enhance signals from short-range order and how a vortex beam can be used to characterize local symmetry., Competing Interests: Conflict of Interest The authors declare that they have no competing interest., (© The Author(s) 2023. Published by Oxford University Press on behalf of the Microscopy Society of America. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Scanning transmission electron microscopy tomography with ChromEM staining (ChromSTEM), has allowed for the three-dimensional study of genome organization. By leveraging convolutional neural networks and molecular dynamics simulations, we have developed a denoising autoencoder (DAE) capable of postprocessing experimental ChromSTEM images to provide nucleosome-level resolution. Our DAE is trained on synthetic images generated from simulations of the chromatin fiber using the 1-cylinder per nucleosome (1CPN) model of chromatin. We find that our DAE is capable of removing noise commonly found in high-angle annular dark field (HAADF) STEM experiments and is able to learn structural features driven by the physics of chromatin folding. The DAE outperforms other well-known denoising algorithms without degradation of structural features and permits the resolution of α-tetrahedron tetranucleosome motifs that induce local chromatin compaction and mediate DNA accessibility. Notably, we find no evidence for the 30 nm fiber, which has been suggested to serve as the higher-order structure of the chromatin fiber. This approach provides high-resolution STEM images that allow for the resolution of single nucleosomes and organized domains within chromatin dense regions comprising of folding motifs that modulate the accessibility of DNA to external biological machinery., Competing Interests: The authors declare the following competing financial interest(s): A.L.F. is a co-founder and consultant of Evozyne, Inc. and a co-author of US Patent Applications 16/887,710 and 17/642,582, US Provisional Patent Applications 62/853,919, 62/900,420, 63/314,898, and 63/479,378 and International Patent Applications PCT/US2020/035206 and PCT/US2020/050466., (© 2023 The Authors. Published by American Chemical Society.)