Recent lbnl_es items

Electrode-omics reveals epochs in silicon anode evolution underpinning electrochemomechanical resilience

Tue, 4 Aug 2026 00:00:00 +0000

Here, we advance electrode-omics to identify evolutionary bursts by which ethereal locally superconcentrated electrolytes (LSCEs) mitigate silicon anode degradation through its epochs of electrochemical and chemical reactions. Anode composites form initially at high potential from ethereal solvent and anion [bis(fluorosulfonyl)imide (FSI^-)] redox. A first evolutionary burst at lower potential enriches composites with lithium alkoxides (LiO-R) and lithium oxide (Li₂O) and depletes sulfur oxides (SO_x) species. As the cells are cycled, a second evolutionary burst takes place, where previously extinct SO_x species reemerge concurrently with a loss of LiO-R and Li₂O. This identifies reactions rooted in "SuFEx" chemistry, where oxoanionic LiO-R and Li₂O species, electrochemically generated in the solid-electrolyte interphase, chemically react with FSI^- in the electrolyte to form emergent species....

Structure of iridium oxide catalysts dictates performance differences for proton exchange membrane water electrolyzers

Fri, 31 Jul 2026 00:00:00 +0000

A systematic catalyst loading study reveals the higher catalytic activity of amorphous iridium oxide arises from bulk participation via suggested electrochemical descriptors, while identifying loading-independent intrinsic electrochemical properties. Proton exchange membrane water electrolyzers (PEMWEs) are promising zero-emission technologies. However, their high cost remains a barrier to widespread adoption. Iridium oxide is commonly used as an oxygen evolution reaction (OER) catalyst, and its cost and scarcity make it essential to reduce its loading while increasing its activity. Evaluation of iridium oxide activity should be carried out in the membrane electrode assembly (MEA) configuration to replicate realistic operating conditions. Herein, we present a comprehensive benchmarking framework to accurately evaluate the amorphous and crystalline iridium oxides at the MEA level. By systematically varying the catalyst loading, this study confirmed that each MEA was utilized...

High-throughput analysis of total electron yield and outgassing under EUV exposure for accelerated photoresist materials discovery

Thu, 30 Jul 2026 00:00:00 +0000

As technology nodes shrink, extreme ultraviolet (EUV) photoresists are essential for high-resolution nanopatterning. Incident photons, as well as electrons generated during EUV exposure can cause both intended and unintended chemical reactions. Understanding these processes is critical for improving resist performance. This study investigates how resist components, particularly photoacid generators (PAGs) and photo decomposable quenchers (PDQ), influence photon- and electron-induced chemistry. It also aims to develop a high-throughput characterization method for efficient screening of novel materials. A high-throughput system combining total electron yield (TEY) and residual gas analysis (RGA) was developed. TEY measures electron generation and capture, while RGA monitors chemical transformations via outgassing. The method is applied to model resists. TEY and outgassing analysis revealed that PAGs and PDQs strongly influence electron behavior and outgassing characteristics. The...

Attosecond response of molecules to impulsive ionization

Wed, 29 Jul 2026 00:00:00 +0000

When matter interacts with energetic radiation it can undergo sudden, or impulsive, ionization. This process can drive chemical change and occurs widely in space and planetary atmospheres, yet its comprehensive description challenges our current theoretical and computational capabilities as it requires advanced treatment of electron correlation and nonadiabatic dynamics beyond the Born–Oppenheimer approximation. Here we measure the response of the para-aminophenol molecule to sudden ionization. Using attosecond X-ray absorption spectroscopy, we resolve the ultrafast dynamics of the ionized molecule with atomic precision. A subfemtosecond decay corresponds to states undergoing non-radiative decay, whereas few-femtosecond oscillatory signatures are associated with electronic wavepacket motion in stable cation states that later couple to nuclear motion. We compare our measurement with state-of-the-art computational modelling, qualitatively reproducing the observed response across...

Toward Hydrogen Isotope Separations through Strong Hydrogen Adsorption at Open Copper(I) Sites in an Ultramicroporous Metal–Organic Framework

Wed, 29 Jul 2026 00:00:00 +0000

Metal-organic frameworks with coordinatively unsaturated metal sites (open metal sites) capable of engaging in orbital interactions with π-acidic gases are of interest for enabling ambient-temperature gas separations, such as hydrogen isotope separations. In view of the weakly π-acidic nature of H₂, we sought to strengthen π-backbonding-mediated H₂ adsorption through pore confinement effects. Toward that end, we synthesized and characterized the ultramicroporous metal-organic framework Cu_xZn_5-xCl_4-yH_z(bbta)₃ (Cu^IZn-MFU-4; H₂bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole), featuring π-basic trigonal pyramidal Cu^I sites that reside within 7 Å of one another at their closest. Gas adsorption measurements reveal an H₂ adsorption enthalpy of -38 kJ/mol, exceeding that of the larger-pore analog (Cu^IZn-MFU-4l;...

Identifying Strain Stacking Boundaries between Multiphase Domains in Atomically Thin Two-Dimensional Magnets

Wed, 29 Jul 2026 00:00:00 +0000

Stacking engineering of van der Waals materials is an important strategy to control the materials' properties, such as electronic correlations, ferroelectricity, and layer-dependent two-dimensional magnetism. A timely testbed for the study of the latter is atomically thin chromium trihalides (CrX₃, X = Cl, Br, I). Notably, by understanding the sliding mechanism between different stacking sequences, control of the stacking arrangement, and thus magnetic properties in CrX₃, can be achieved. Such insight, however, is currently lacking. Here, advanced electron microscopy methods are used to identify multiple stacking sequences corresponding to different bulk phases in atomically thin CrX₃ (X = Cl and Br) down to bilayer thickness and with lateral domain sizes as small as tens of nanometers. Indications of nanometer scale transitions and interactions at the stacking boundaries are found, including a universally preferred sliding direction that is consistent...

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Wed, 29 Jul 2026 00:00:00 +0000

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases...

Electrostatic‐Attraction‐Driven Self‐Assembled Graphene‐Disordered Rocksalt Composite Cathode for Lithium‐Ion Batteries

Wed, 29 Jul 2026 00:00:00 +0000

ABSTRACT Disordered rocksalt cathodes hold promise for achieving high‐capacity lithium‐ion batteries while using low‐cost, earth‐abundant elements. However, their electrochemical performance remains critically limited by their poor electronic conductivity. Conventional strategies such as high‐energy ball milling with excess carbon additives can improve conductivity but remain challenging to scale and often produce defects and increase surface area, thereby accelerating capacity degradation. Herein, we report an alternative approach of electrostatic‐attraction‐driven self‐assembly to fabricate Li 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 (LMTOF) particles uniformly wrapped with electronically conductive graphene sheets without associated materials degradation. The graphene‐wrapped LMTOF demonstrates significantly improved cycling stability (89% capacity retention after 100 cycles) and superior rate capability compared with an LMTOF‐carbon composite electrode fabricated using the conventional...

The Use of Synchrotron Radiation in the Medical Sciences

Tue, 28 Jul 2026 00:00:00 +0000

Synchrotron radiation (SR) sources provide unparalleled brilliance, collimation, coherence, and tunability, enabling specialized techniques that are crucial for advancing medical research across diverse fields from radiation oncology to rational drug design. Certain SR methods, such as macromolecular crystallography, are highly developed and automated, and have been used for decades for both fundamental understanding of biomolecules as well as pharmaceutical design, while other methods, such as microbeam radiation therapy, represent relatively recent developments. Scattering and diffraction methods using SR can provide atomic-level structural mapping of proteins, nucleic acids, and complexes. Imaging applications using SR continue to be developed and advanced for mapping of biological structures and potential use as diagnostics in disease detection. Spectroscopic methods are used to study elemental distributions relevant for detection of contamination in biological systems. Collectively,...

Mineralized tissue of shark vertebral centra studied with microCT under in situ load

Tue, 28 Jul 2026 00:00:00 +0000

Shark vertebral bodies (centra) possess remarkable resistance to millions of cycles of large in vivo strains exceeding 4 to 8%. These strains are enormous for a mineralized tissue, and it appears that the centra evolved to achieve this performance through a hierarchy of structures spanning dimensions from centimeters to nanometers. At the 1μm scale, blocks cut from centra and imaged with synchrotron microCT demonstrate that the centra tissue consists of closely spaced, mineralized trabeculae. An outstanding question is: How do these trabeculae deform to accommodate these large strains. This paper presents recently obtained synchrotron microCT results on in situ loading of blocks of shark centra and examines the deformation modes of the interconnected array of trabeculae.

Catalytic visible light-driven alkane dehydrogenation by a di-uranyl germanotungstate

Tue, 28 Jul 2026 00:00:00 +0000

The dehydrogenation of alkanes to alkenes is an appealing strategy for upgrading abundant hydrocarbons, yet it is constrained by the inherent challenge of cleaving two inert C(sp³)-H bonds with selectivity and without overoxidation. We report a cooperative photocatalytic dehydrogenation of unactivated cycloalkanes under visible light irradiation enabled by a new dinuclear uranyl complex supported by an oxidatively stable germanotungstate, [NBu ⁿ ₄]₈[(UO₂)₂(GeW₁₀O₃₄(µ₂-OH)₂)₂]·(CH₃)₂CO (1). The uranyl complex catalytically converts cyclooctane to cyclooctene under ambient conditions with a TON per molecule of 44 and 9,10-dihydrophenanthrene to phenanthrene with a TON of 73 per molecule, using 1 mol% 1 in MeCN solution, under 427 nm irradiation, using [S₂O₈]^2- or chloranil (C₆Cl₄O₂)...

Catalytic Ambient Temperature Dinitrogen Conversion to a Bis(silyl)amine by Mononuclear Group 4 Aryloxide Complexes

Tue, 28 Jul 2026 00:00:00 +0000

The homogeneous conversion of ambient dinitrogen to amine products via the N₂ reduction reaction (N₂RR) remains a prized yet challenging feat for d-block complexes and is scarcely reported for f-block complexes. New, mononuclear Ti^IV and Zr^IV aryloxide complexes Ti(DP)₂ (1Ti), Zr(DP)₂ (1Zr), and DP = [2-(OC₆H₂-2-^tBu,4-Me)₂CHPh] produce up to 51 eq. and up to 7.0 eq. of HN(SiMe₃)₂ per Ti/Zr, from N₂, K⁰, weak acid, and chlorotrimethylsilane. Complex 1Ti exhibits more than double the activity toward N₂-silylation of any previously reported Ti N₂RR catalyst and can also catalyze the formation of up to 19 eq. of NH₃, a new feature in early metal N₂RR chemistry. The mononuclear 1Zr is the most active Zr catalyst for N₂-silylation to date. [KSm(DP)₂(THF)₃]...

Recommendations and considerations for hydroxyl radical protein footprinting–mass spectrometry

Tue, 28 Jul 2026 00:00:00 +0000

Protein oxidative footprinting, using hydroxyl radical labeling detected by bottom-up proteomics, has progressed from an emerging method to a widely used approach in structural biology. Hydroxyl radicals generated from hydrogen peroxide (via photolysis, Fenton chemistry or electrochemistry) or directly from water (via X-rays, plasma or gamma rays) irreversibly encode structural information within protein side chains, which is read out using standard liquid chromatography–mass spectrometry workflows. Quantitative changes in labeling report on solvent accessibility and reveal effects of protein–protein interactions, ligand binding, protein folding, conformational changes or applied stress. Comparing labeling patterns between states provides detailed maps of structural changes and interaction sites. Over the past decade, oxidative footprinting has proven valuable as a solution-phase and in-cell method for protein structure analysis. This Perspective summarizes best practices for...

Universal Relationship between Limiting Current and Electrochemical Transport Properties in Malonate-Based Polymer Electrolytes

Tue, 28 Jul 2026 00:00:00 +0000

There is considerable interest in developing high-performance electrolytes for rechargeable lithium batteries. For practical applications, the electrolyte must support large dc currents. However, the parameters most often reported in the literature, conductivity, κ, and current fraction, ρ+, reflect ion transport in the limit of infinitesimal currents. In this limit, the efficacy of an electrolyte is given by the product κρ+. The limiting current density, i lim, is the maximum current density that can be applied across an electrolyte; the cell voltage diverges if the applied current density exceeds i lim. This parameter reflects ion transport in the limit of large dc currents and is therefore of practical interest. It would therefore be convenient if i lim could be predicted from measurements of κρ+. In order to explore this possibility, we studied six malonate-based polymers and PEO at a fixed salt concentration (r = 0.08) and temperature (90°C) using symmetric cells with planar...

Two-component exciton condensates in an electron–hole bilayer

Mon, 27 Jul 2026 00:00:00 +0000

Macroscopic quantum coherence emerges when bosons condense into a Bose–Einstein condensate (BEC)1, 2, 3, 4–5. Excitons are a long-sought solid-state route to high-temperature BECs with strong interactions, electrical tunability and potentially multicomponent spinor order, but conclusive evidence for equilibrium condensation has remained elusive. Here we report evidence for two-component exciton BECs in MoSe2/hBN/WSe2 electron–hole bilayers6, 7, 8–9 by probing the spin–valley susceptibility of constituent electrons and holes. This heterostructure hosts equilibrium exciton fluids with four spin–valley flavours. Magneto-optical spectroscopy in a dilution refrigerator reveals three exciton condensate phases with distinct flavour polarizations. At zero magnetic field, the many-body ground state is a coherent superposition of two condensed intravalley exciton flavours. Under a magnetic field, the intravalley exciton condensate first switches to a two-component intervalley condensate...

Unsupervised Segmentation and Clustering Workflow for Efficient Processing of 4D-STEM and 5D-STEM Data

Mon, 27 Jul 2026 00:00:00 +0000

Four-dimensional scanning transmission electron microscopy (4D-STEM) enables mapping of diffraction information with nanometer-scale spatial resolution, offering detailed insight into local structure, orientation, and strain. However, as data dimensionality and sampling density increase, particularly for in situ scanning diffraction experiments (5D-STEM), robust segmentation of structurally consistent behavior across sequential measurements becomes essential for efficient and physically meaningful analysis. Here, we introduce a clustering framework that identifies crystallographically distinct domains from 4D-STEM datasets. By using local diffraction-pattern similarity as a metric, the method extracts closed contours delineating spatially contiguous regions. This approach produces cluster-averaged diffraction patterns that improve signal quality while reducing data volume by orders of magnitude, enabling rapid and accurate orientation, phase, and strain mapping. We demonstrate...

Structure of domain walls in chiral spin liquids.

Mon, 27 Jul 2026 00:00:00 +0000

The chiral spin liquid is a canonical state of quantum spins combining topological and symmetry-breaking order, and possible experimental realizations have attracted growing interest. We examine the physics at interfaces between chiral spin liquid domains of opposite chirality. We show that a self-consistent mean-field description of spinons remains possible in the vicinity of a domain wall and use this to formulate a Ginzburg-Landau theory of the domain wall. The bulk of a chiral spin liquid contains gapped spinon excitations and gauge fluctuations, set by a finite spinon mass and a nonzero spinon Chern number. A third class of excitations consists of amplitude fluctuations of the spinon hoppings, which admit a geometric interpretation in terms of effective vielbein fields. These fluctuations are usually neglected because they are irrelevant for a homogeneous chiral spin liquid and are suppressed in standard large-[Formula: see text] treatments. Going beyond the purely topological...

Mechanisms of Alkali Ionic Transport in Amorphous Oxyhalides Solid State Conductors

Mon, 27 Jul 2026 00:00:00 +0000

ABSTRACT Amorphous oxyhalides have attracted significant attention due to their relatively high ionic conductivity (1 mS ), excellent chemical stability, mechanical softness, and facile synthesis routes via standard solid‐state reactions. These materials exhibit an ionic conductivity that is almost independent of the underlying chemistry, in stark contrast to what occurs in crystalline conductors. In this work, we employ machine learning interatomic potentials to construct large‐scale molecular dynamics trajectories encompassing hundreds of nanoseconds to obtain statistically converged transport properties. We find that the amorphous state consists of chain fragments of metal‐anion tetrahedra of various lengths. By analyzing the residence time of alkali cations migrating around tetrahedrally‐coordinated metals, we find that oxygen anions limit alkali diffusion. By computing the full Einstein expression of the ionic conductivity, we demonstrate that the alkali transference number...

Amphiphilic Baskets for Supramolecular Nanoarchitectures at Interfaces: Inverted Monolayer Formation on Water

Mon, 27 Jul 2026 00:00:00 +0000

Interfacial chemistry of molecular baskets remains poorly understood despite their promise for supramolecular applications of detection and sequestration of toxic molecules including those of illicit drugs, organophosphorus compounds, and anticancer agents. We present a fundamental investigation of the interfacial behavior of three amphiphilic supramolecular baskets (ASB 4, 8, and 12), having increasingly longer yet linear alkyl chains at the top of their bowl-shaped cavity. The studies were completed at the air-water interface to elucidate surface activity, interfacial stability, self-assembly, and monolayer organization that drive inverted monolayer formation, in which the molecular arms orient toward the aqueous phase in a configuration opposite to that typically observed for lipids. Herein, surface pressure-area isotherms of ASB 4, 8, 12, deposited on a water surface, were performed in tandem with nonequilibrium relaxation experiments to quantify surface activity, thermodynamic...

Scalable multiplexed machine learning gas sensor chips for food classification