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At least 37 records · Page 2

Correlating Surface Processing of Nb Superconducting RF Cavities with the Evolution of Surface Electronic States

Superconducting-radio frequency (RF) cavities provide an efficient way to accelerate particle beams with extremely high acceleration gradients while generating very small power dissipation. The few nanometers of the surface play a critical role in defining the RF performance of superconducting Nb based cavities. Over the past two decades, several pioneering surface treatment and processing methods have emerged, enabling remarkable improvements in superconducting cavity performance by simultaneously achieving high quality factors with increasing maximum acceleration gradients. These processing approaches include chemical polishing, distinct multi-step thermal treatments under ultra-high vacuum (UHV) conditions over low to high temperature regimes, as well as high-temperature treatments under controlled nitrogen atmospheres. Beyond their macroscopic impact on RF performance, these methods produce distinct surface oxide configurations characterized by different valence states, oxide thicknesses, chemical uniformity, and oxygen concentration profiles extending into the near-surface bulk of niobium. In this work, we are trying to understand how the surface-processing methods and the resulting oxide/oxygen profiles affect the electronic structure of surface and the mechanism of superconductivity. Using a combination of X-ray photoemission and X-ray absorption spectroscopies, we investigate how the valence-band structure and the electronic density of states (DoS) near the Fermi level evolve under different surface treatments. By employing tunable photon energies across multiple elemental absorption edges, we use resonant photoemission to disentangle and identify the elemental contributions to specific valence-band features. Our observations show that different surface-processing methods lead to distinct temperature evolutions of the DoS and valence-band states near the Fermi level. Our results suggest variations in different Nb-O orbital hybridizations in distinct processes and point towards the possibility of different underlying mechanisms of superconductivity governed by surface chemistry and oxide configuration. We also correlate these distinct superconducting mechanisms with RF cavity performance, specifically focusing on measured surface resistance, the nature of the Q-slope, and quench fields observed in superconducting RF measurements. These results will enable us to identify the potential limiting factors and relevant controllable parameters that can be further optimized to improve the performance of superconducting RF cavities.

Tripathi, Malvika [Fermilab] (ORCID:00000001989251↗

Structure of Complex Liquid–Liquid Extraction Organic Phases for Rare Earth Separations

Complex, multicomponent liquids with hierarchical structure and phase transitions are encountered in many natural and industrial processes, including in chemical separations. One notable example is aggregation and organic phase splitting in liquid–liquid extraction (LLE) of metal ions. While these two phenomena that have long been closely associated, a mechanistic link between mesoscale structure and the capacity-limiting organic phase splitting remains elusive due to complexity of these systems. Here, in this study, we combine small-angle X-ray scattering (SAXS), X-ray photon correlation spectroscopy (XPCS), and molecular dynamics simulation to reveal a comprehensive picture of structure at the nano- and mesoscale in these complex solutions. For the representative case of rare earth extraction from an acidic aqueous phase by a malonamide extractant in dodecane, we investigate a wide range of process-relevant extractant and acid concentrations to provide a complete picture of how aggregation depends on composition. We decompose organic phase structure from SAXS into two contributions, which together can capture the scattering at all compositions: composition fluctuations described by the Ornstein–Zernike equation at low wavenumber Q, and nanostructure modeled by a “pre-peak” at intermediate Q. The former contains information about the thermodynamics of demixing, while the latter reflects nanoscopic self-assembly of the extractant and extracted solutes. While fluctuations have typically not been considered in the literature, we find they in fact dominate the total structure for nearly all practical conditions. As only the fluctuations have a strong temperature response, we confirm this attribution with temperature-dependent SAXS measurements, including for extracted europium nitrate complexes. SAXS and XPCS measurements near the critical point find static and dynamic scaling consistent with theory. Overall, this new paradigm for understanding LLE organic phases connects composition, nanoscale, and mesoscale structuring to phase behavior, providing both a comprehensive picture of solution structure and a quantitative link between aggregation and third phase formation.

Peroutka, Allison A. [Argonne National Laboratory ↗

Lunar elemental analysis obtained from the Apollo gamma-ray and X-ray remote sensing experiment

Gamma-ray and X-ray spectrometers carried in the service modules of the Apollo 15 and Apollo 16 spacecraft were employed for compositional mapping of the lunar surface. The measurements involved the observation of the intensity and characteristic energy distribution of gamma rays and X-rays emitted from the lunar surface. A large-scale compositional map of over 10 percent of the lunar surface was obtained from an analysis of the observed spectra. The objective of the X-ray experiment was to measure the K spectral lines from Mg, Al, and Si. Spectra were obtained and the data were reduced to Al/Si and Mg/Si intensity ratios and ultimately to chemical ratios. Analyses of the results have indicated (1) that the Al/Si ratios are highest in the lunar highlands and considerably lower in the maria, and (2) that the Mg/Si concentrations generally show the opposite relationship. The objective of the gamma-ray experiment was to measure the natural and cosmic-ray-induced activity emission spectrum. At this time, the elemental abundances for Th, U, K, Fe, Ti, Si, and O have been determined over a number of major lunar regions. Regions of relatively high natural radioactivity were found in the Mare Imbrium and Oceanus Procellarum regions.

Trombka, J. I.↗

Pressure-induced changes in structure, magnetic order and superconductivity in the ferromagnetic topological insulator MnBi 8 Te 13

Introducing superconductivity (SC) in an intrinsic magnetic topological system remains a significant challenge in modern condensed matter physics. Here, we show that SC can be induced by applying high pressure to a promising ambient-pressure magnetic topological insulator candidate, MnBi 8 Te 13 . Using electrical transport, magnetic susceptibility, and synchrotron x-ray diffraction, we construct a detailed temperature - pressure phase diagram. The ambient-pressure ferromagnetic order is progressively suppressed and replaced by an antiferromagnetic state. Above 16.6 GPa, bulk SC emerges with a critical temperature up to 6.8 K. This pressure-induced SC may co-exist with another AFM dome. In contrast, the related compounds with higher magnetic ion (Mn) concentration show no SC, highlighting the crucial role of Mn concentration in stabilizing SC. The observation of pressure-induced FM-AFM-SC transitions in MnBi 8 Te 13 not only establishes it as a rare Mn-based SC but also provides a platform to study the interplay between magnetism, SC, and potentially nontrivial band topology in correlated magnetic materials.

Huyan, S. [Ames Laboratory, and Iowa State Univ., ↗

Dissecting Disorder: Defect-Driven Structural Complexity in Layered Li3InCl6 Solid Electrolyte

Halide solid electrolytes have emerged as promising candidates for solid-state batteries owing to their high oxidative stability and ionic conductivity. Among them, Li3InCl6 (LIC) has attracted significant attention. However, diffraction patterns of LIC synthesized via different methods exhibit distinct differences particularly at low-angle reflectionsindicative of underlying structural disorder. These variations are attributed to deviations from ideal crystallographic order, especially stacking faults, whose impact on structure and ion transport remains poorly understood. Here, we identify and quantify stacking faults in LIC samples prepared under different synthetic conditions. Using X-ray diffraction and time-of-flight neutron diffraction, we construct and refine stacking fault models that accurately reproduce the experimental diffraction features. LIC samples with higher degrees of stacking faults exhibit only negligible differences in ionic conductivities and activation energies. This indicates that stacking faults have a limited impact on altering the Li+ diffusion pathway along the c-axis, likely due to the high concentration of vacancies in the In layers, while Li+ diffusion remains nearly unchanged in the ab-plane. Our results account for the observed differences in diffraction patterns across samples and provide a quantitative assessment of faulting probabilities and stacking sequences. The insights gained from this study are expected to be broadly applicable to other layered halide solid electrolytes and contribute to a deeper understanding of the role of structural disorder in ion transport.

Liu, Jue [ORNL] (ORCID:000000024453910X)↗

Coupled Chemical and Mechanical Control of Phase Stability in Lanthanide-Substituted BiVO 4

Doping is widely used to enhance the photoelectrochemical performance of BiVO 4 , yet solubility limits and polymorphic stability constrain compositional tuning. Here, in this study, the role of trivalent cation substitution (Ln = La, Nd, Dy, Ho, Y) on pressure-induced phase transformations in Bi 1–x Ln x VO 4 (x ≤ 0.5) is described. Powder X-ray and neutron diffraction reveal that increasing Ln content stabilizes the tetragonal zircon-type polymorph under ambient conditions, while applied pressures of up to ∼5 GPa promote conversion to the monoclinic fergusonite-type polymorph. In-situ neutron diffraction on Bi 0.8 La 0.2 VO 4 shows a reversible monoclinic to tetragonal transition near 2–3 GPa with a bulk modulus of 147 GPa. The extent of conversion depends strongly on dopant identity, concentration, and synthetic route, with mixed-phase solid-state samples converting more efficiently than phase-pure coprecipitated materials. These results demonstrate pressure as a viable pathway to access metastable, doped BiVO 4 compositions beyond conventional solubility limits.

Sypkes, Kathryn I. [University of Sydney, NSW (Aus↗

Optimizing Porous Transport Layer Porosity for Proton Exchange Membrane Water Electrolysis

An empirical model is presented that describes anode-side losses related to porous transport layer (PTL) morphology in proton exchange membrane water electrolysis (PEMWE). The model is based on an advanced voltage breakdown analysis that links various overpotentials to PTL morphology. Custom Ti PTLs, spanning uncommonly low porosities (22 - 31%), were fabricated and analyzed with X-ray CT to obtain pore and particle size distributions. Particle size distributions were consistent across samples with an average particle diameter of 12.0?..mu..m, whereas average pore diameters ranged from 6.0 to 7.0?..mu..m. The PTLs were tested in standard PEMWE cell assemblies with anode catalyst loadings of 0.1 mgIr cm-2 to obtain polarization curves, electrochemical impedance spectra, and augmented Tafel analysis. The PTL-dependent anode side losses were deconvoluted and assigned to excess utilization, concentration, ion transport resistance, and electrical contact resistance overpotentials. The data and model reveal an optimal 20 - 28% PTL porosity region where utilization and contact resistance overpotentials are minimized without triggering concentration and ion transport losses related to water deprivation. The optimal PTL porosity depends on the operating current density and is demonstrated at realistic PEMWE water flow rates to establish PTL design guidance for operation at scale.

08 HYDROGEN↗

Limited proteolysis of pea protein to promote aggregation/gelation: role of enzyme concentration and molecular characteristics

Limited proteolysis promotes aggregation/gelation of plant proteins, but its relationship with the molecular characteristics of hydrolysates remains poorly understood. In here, response surface methodology was employed to evaluate the effects of protein concentration, Alcalase level, and hydrolysis time on the storage modulus (G′) of pea protein hydrolysates (PPH). 7.5% protein, 1.65% Alcalase, and a 6-min reaction time resulted in the highest relative increase in G′ upon heating PPH, whereas both higher (3.55%) and lower (0.3%) Alcalase levels led to less increment. Increasing the Alcalase level increased the degree of hydrolysis while decreasing the molecular weight, surface hydrophobicity, and total sulfhydryl and disulfide bond contents of PPH. Confocal laser scanning microscopy and X-ray scattering analyses found PPH produced with 1.65% Alcalase formed interconnected aggregates with dual structural domains, but not at other Alcalase conditions. These results demonstrate the role of controlled proteolysis in governing the aggregation/gelation behavior of PPH.

X-ray scattering↗

Mechanisms of Metal Additive-Induced Ordering During SNIPS Membrane Formation

Isoporous membranes can be fabricated by combining self-assembly with nonsolvent induced phase separation (SNIPS) using an amphiphilic block copolymer like polystyrene-b-poly(4-vinylpyridine) (SV). Poly(4-vinylpyridine) (V) is known to complex with metal salts, which are hypothesized to stabilize solution ordering and preserve structure during casting. We explored how the molar ratio of metal additive to the poly(4-vinylpyridine) block affected the final membrane morphology via scanning electron microscopy (SEM). Dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and in situ grazing-incidence SAXS were used to track changes in solution ordering and chain conformation as a function of the molar ratio of the additive to the V block. Additives induced aggregation, promoted the formation of more compact conformations in solution, and facilitated micelle ordering onto lattices at optimal ratios. Furthermore, these experimental results were supported by random phase approximation calculations, which helped explain how the thermodynamic order–disorder transition shifts with additive binding strength. Stronger additive–polymer interactions reduced the block copolymer volume fraction required for ordering in solution, allowing ordered domains to form at lower polymer concentrations.

Additives↗

Separation and Recovery of High-Purity Dysprosium from Electric Vehicle Scrap Permanent Magnets Using Cyanex 572, a Cationic Extractant in a Membrane Solvent Extraction Process

Rare earth elements (REEs), especially heavy rare earth elements such as dysprosium (Dy), have gained immense attention globally due to their widespread use in many state-of-the-art technologies. Consequently, demand for REEs is increasing rapidly in comparison to their supply. Recycling of REEs from end-of-life (EoL) electronic waste (e-waste) can help to mitigate the increasing gap between the demand and supply of REEs. This study reports the separation and recovery of high-purity Dy from various feedstocks such as scrap permanent magnets (SPMs), electric vehicle (EV) magnets, and mixed rare earth oxides (REOs) using an economically viable and scalable membrane solvent extraction (MSX) process. First, the optimized conditions (organic phase composition and feed solution acid concentration) for the separation of Dy from light REEs such as neodymium (Nd) and praseodymium (Pr) were evaluated using liquid–liquid extraction. Thereafter, a multistage MSX process was developed to separate high purity (>99.5 wt %) Dy from Nd and Pr using Cyanex 572, a cationic extractant. Using feedstocks with varying initial compositions, the MSX process obtained 100% pure Dy with 63–96% Dy recovery in three to six stages with a maximum extraction rate of 2.9 g m–2 h –1 . Purity of the recovered Dy was confirmed via additional characterization such as scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. This novel MSX process holds immense potential for industry deployment for the separation of heavy and light rare REEs from a wide range of e-waste.

electrical vehicle magnets↗

Task Sharing of Proton Incorporation in Vertically Aligned Nanocomposite Triple Conductors: Growth, Structure, and Surface Exchange Kinetics

As protonic ceramic electrolysis cells emerge for efficient H 2 production, there is a need to develop air electrode materials enabling fast, durable steam splitting and proton incorporation. Single-phase triple conductors may fail to satisfy the myriad performance/stability requirements, and their critical charge-carriers (holes, oxygen vacancies, and protons) are in competition, limiting their concentrations. Instead, we propose task-sharing, vertically aligned nanocomposites (VANs), comprising a proton conductor (BaZr 0.9 Y 0.1 O 3-δ ) and a redox-active mixed ionic electronic conductor (Ce 0.9 Pr 0.1 O 2-δ ), that may enable rapid proton surface exchange at the solid–gas interface and transport along the solid–solid heterointerfaces. We grew VANs by pulsed laser deposition and investigated the interplay between their processing conditions, structure, and proton and oxygen surface exchange kinetics. We varied the substrate temperature, laser repetition rate, laser fluence, and processing oxygen pressure. The crystallinity and phases were characterized by grazing-incidence X-ray diffraction, and the strain and structural order as a function of depth were evaluated by angle-dependent synchrotron X-ray pair distribution function analysis. To evaluate the potential for interdiffusion, the formation energies of substitutional defects were simulated with density functional theory. Corresponding structural analysis and elemental mapping were performed by scanning/transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy-loss spectroscopy, indicating distinct nanoscale compositional regions with a hierarchical structure embedded in individual VANs columns and minimal interdiffusion across a bilayer film. Proton and oxygen surface exchange coefficients (k H , k O ) and polarization resistances were evaluated by electrical and optical relaxations and impedance spectroscopy of VAN-incorporated protonic ceramic electrochemical cells, respectively, at 400–500 °C, demonstrating values comparable to some of the best-known triple and mixed conductors.

36 MATERIALS SCIENCE↗

Thermal Inspection for the Assessment of Adhesively Bonded Metal Adherends

Certification of adhesively bonded structures is currently a challenge for aircraft manufacturers. The ability to certify bonds in primary structure can reduce dependence on fasteners and this will enable more efficient manufacturing. For example, drilling holes and installing fasteners in bonded joints can be a potentially significant bottleneck in airframe manufacturing. In addition, fasteners increase the airframe weight and can add stress concentration areas. Reducing fastener count can accelerate manufacturing and improve aircraft performance. NASA is currently investigating nondestructive evaluation (NDE) techniques to assess bond integrity. For example, bond thickness influences bond strength and therefore NDE techniques are being investigated to determine bond thickness. For bonded metal structures, there is a large difference in the thermal diffusivity between the 7075 aluminum alloy metal adherends and aircraft grade adhesive. Multi-layered thermal models show a large variation in the thermal response for bondline adhesive thicknesses that vary from 100 to 300 microns for adherend thicknesses of 0.163 cm. Experimental through-transmission thermal measurements reveal promise to quantitatively characterize the bondline thickness. Results were validated with X-ray computed tomography and optical microscopy measurements, and influence of porosity on the thermal model and measurements are investigated.

X-ray computed tomography↗

Thermal Inspection for the Assessment of Adhesively Bonded Metal Adherents

Certification of adhesively bonded structures is currently a challenge for aircraft manufacturers. The ability to certify bonds in primary structure can reduce dependence on fasteners and this will enable more efficient manufacturing. For example, drilling holes and installing fasteners in bonded joints can be a potentially significant bottleneck in airframe manufacturing. In addition, fasteners increase the airframe weight and can add stress concentration areas. Reducing fastener count can accelerate manufacturing and improve aircraft performance. NASA is currently investigating nondestructive evaluation (NDE) techniques to assess bond integrity. For example, bond thickness influences bond strength and therefore NDE techniques are being investigated to determine bond thickness. For bonded metal structures, there is a large difference in the thermal diffusivity between the 7075 aluminum alloy metal adherends and aircraft grade adhesive. Multi-layered thermal models show a large variation in the thermal response for bondline adhesive thicknesses that vary from 100 to 300 microns for adherend thicknesses of 0.163 cm. Experimental through-transmission thermal measurements reveal promise to quantitatively characterize the bondline thickness. Results were validated with X-ray computed tomography and optical microscopy measurements, and influence of porosity on the thermal model and measurements are investigated.

bondline thickness↗

Speciation of Transition Metal Dissolution in Electrolyte from Common Cathode Materials

Significant capacity loss has been observed across extended cycling of lithium-ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid-electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. Here, in this work, X-ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 (LNMO), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and (x Li 2 MnO 3 *(1-x) LiNi a Mn b Co c O 2 , with a+b+c=1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma-mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.

25 ENERGY STORAGE↗

Impact of nitrogen on lithium-induced corrosion and cracking of RAFM steel

The emergence of private fusion enterprises, combined with advancements in U.S. and EU ITER-TBM as well as EU DEMO liquid breeder blanket concepts, has renewed focus on the materials challenges. This study examines the compatibility of reduced activation ferritic/martensitic (RAFM) steel in liquid Lithium (Li) containing various Nitrogen (N) concentrations, tested at 600 and 700 °C for 500 and 1000 h under static conditions. Microstructural characterization revealed the corrosion-induced dissolution and precipitation in Li containing 0.082 and 0.17 wt.% N at 600 °C, while limited dissolution and precipitation were observed in N-gettered Li using zirconium (Zr) and titanium (Ti) foils at 600 °C. Tensile testing at room temperature after Li exposure revealed a decrease in strength and ductility of the RAFM steel as a function of N content in Li. Severe embrittlement was observed after 500 h in Li containing 0.17 wt.% N at 600 °C and after 500 h in hot-gettered Li at 700 °C. Chromium (Cr) depletion from the steel matrix was observed, leading to the formation of M6C-type carbides on the surface identified by electron microscopy (SEM), X-ray diffraction (XRD), in agreement with thermodynamic calculations. These findings highlight the critical materials challenges posed by liquid Li breeder blanket concepts, emphasizing the need for improved strategies to address Li-induced dissolution, precipitation, and steel embrittlement due to N contamination of the coolant.

Romedenne, Marie [ORNL] (ORCID:0000000317936561)↗

Establishing the Stability of Cross-Linked Poly(ethylene oxide) Blended with Poly(pentyl malonate) against Lithium Metal Anodes

This work focuses on an electrolyte obtained by infusing linear poly(pentyl malonate) (PPM) chains into cross-linked poly(ethylene oxide) (PEO). A lithium salt is added to enable ion transport. Obtaining this electrolyte is only possible because PPM is miscible with PEO irrespective of salt concentration. The properties of this electrolyte are compared against two benchmarks: an electrolyte obtained by infusing linear PEO into cross-linked PEO and cross-linked PEO with no added linear polymer. Measurements of storage moduli and ion transport efficacies are found to be similar across the three electrolytes, suggesting similar stability behavior against lithium metal anodes, based on current theoretical models. Instead, the PPM infused electrolyte outperforms the other two electrolytes. In the cycling tests, the current supported by the PPM infused electrolyte was a factor of 20 higher than that of the PEO infused electrolyte and a factor of 4 higher than that of the cross-linked PEO electrolyte. In the unidirectional plating experiments, the other two electrolytes fail after about 4 h or less, while the PPM containing electrolyte did not fail during the 140 h testing period. Insight into the nature of failure modes was obtained using synchrotron hard X-ray microtomography.

Gido, Lily [University of California, Berkeley]↗

Synthesis, Characterization, and Testing of High-Lithium-Density Composite Breeders

Solid tritium breeder materials must first and foremost have sufficiently high concentrations of lithium to enable a plant-scale tritium breeding ratio greater than 1:1. However, in addition to lithium content, such breeder materials must also meet other performance metrics including high tritium release rates, thermal conductivities, and irradiation damage tolerance. Perhaps most importantly, tritium breeders must maintain their mechanical integrity during reactor operation so as to avoid degradation which can jeopardize the functionality of the tritium breeder blanket module, which in most designs takes the form of a pebble bed geometry. Unfortunately, the mechanical robustness of most lithium-bearing ceramics under investigation for fusion applications is often inversely related to the lithium atom density. For example, a material such as lithium oxide (Li2O), which has one of the highest lithium atom densities, has a much lower mechanical splitting strength than lithium metatitanate (Li2TiO3), though Li2TiO3 has less than half the lithium atom density of Li2O. This work seeks to provide an alternative to monolithic ceramic tritium breeders, in the form of metal-reinforced composite tritium breeders. Specifically, composite tritium breeders have been synthesized combining Li2O with various ferrous metal reinforcements via electric field assisted sintering (EFAS), also known as spark plasma sintering (SPS). As the metal reinforcement content is increased, metallic networks are observed, via electron microscopy and X-ray computed tomography, to form throughout the composite material. Through destructive mechanical testing, even dilute metal reinforcement loading enables drastic mechanical strength improvements over pure Li2O while higher loadings give rise to quasi-ductile behavior and higher ultimate strengths than Li2TiO3 – while still maintaining a higher density of lithium atoms than Li2TiO3 and many other breeder candidates. In addition to microstructural characterization and mechanical testing, thermal property measurements and hydrogen permeability testing are underway to further assess the suitability of such composites for fusion reactor applications.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Synthesis and Characterization of Layered Actinide (U, Np, Pu) Oxide and Hydroxide Phases

Systematic structural comparisons across the early actinides remain limited by the scarcity of well-defined transuranic layered oxide and oxyhydroxide phases. Here, we report the synthesis and single-crystal characterization of new layered actinide compounds spanning U, Np, and Pu obtained under mild hydrothermal conditions in concentrated alkali hydroxide media. These include hydrated oxides α-Cs 2 U 2 O 7 •0.5H 2 O and Rb 2 An 2 O 7 •0.5H 2 O (An = Np, Pu), oxy-hydroxides Rb 6 [(AnO 2 ) 6 O 8 (OH) 2 ]•xH 2 O x = 0, 0.5 (An = U, Np) and Rb 4 [(UO 2 ) 5 O 6 (OH) 2 ]•2H 2 O, as well as nitrate-intercalated compounds Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 (An = Np, Pu). Single-crystal X-ray diffraction studies reveal extended two-dimensional architectures constructed from edge- and vertex-sharing actinyl polyhedra, with systematic evolution in equatorial coordination, hydration, and anionic sheet topology across the U–Np–Pu series. Incorporation of nitrate anions within the interlayer region of Cs 6 [(AnO 2 ) 3 O 4 (OH) 2 ](NO 3 ) 2 establishes a previously unobserved structural motif in layered transuranic oxyhydroxides, demonstrating an additional pathway for anion-mediated framework stabilization. Correlation of crystallographic metrics with single-crystal Raman spectroscopy provides new vibrational benchmarks linking differences in An═O yl bond lengths to the equatorial coordination and the interstitial cations. These findings expand the structural hierarchy of layered actinide materials and address clarifying periodic trends governing topology, bonding, and vibrational signatures in high-valent 5ƒ oxide systems.

actinides↗