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At least 1,657 records · Page 92
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Deterministic Control of Sn 3+ Valence and Electronic Phase Evolution in AgSnSe 2

Understanding how unusual oxidation states influence material properties is important for both fundamental science and energy applications. AgSnSe 2 is particularly intriguing because it stabilizes the rare and long-debated Sn 3+ oxidation state, whose true existence and role have remained enigmatic for many years. Here, in this work, we employ X-ray photoelectron spectroscopy, Mössbauer spectroscopy, and X-ray absorption spectroscopy to directly probe the oxidation state of Sn and its evolution under chemical substitution. All experimental evidence consistently confirms the presence of Sn in the +3 oxidation state in AgSnSe 2 . Complementary density functional theory calculations further corroborate this assignment. By substituting Sn with Sb, we systematically control the electronic state and its impact on the material’s physical properties. At low Sb concentrations, AgSnSe 2 retains superconductivity with a transition temperature of ∼5 K, while increasing Sb content deterministically drives a metallic-to-semiconducting transition through progressive suppression of superconductivity. Spectroscopic analyses show that Sb substitution provides deterministic control of the Sn oxidation state, evolving from a uniform +3 configuration in AgSnSe 2 to a mixed +2/+4 valence-skipping regime at higher Sb levels, thereby establishing a direct chemical handle over the material’s electronic phase. This tunability demonstrates that the Sn oxidation state in AgSnSe2 can be precisely engineered through Sb substitution, enabling controlled electronic phase transitions and establishing AgSnSe 2 as a promising platform for quantum and energy-related applications

crystal structure↗
DOE OSTI2025

X-ray crystallographic and hydrogen deuterium exchange studies confirm alternate kinetic models for homolog insulin monomers

Despite the crucial role of various insulin analogs in achieving satisfactory glycemic control, a comprehensive understanding of their in-solution dynamic mechanisms still holds the potential to further optimize rapid insulin analogs, thus significantly improving the well-being of individuals with Type 1 Diabetes. Here, we employed hydrogen-deuterium exchange mass spectrometry to decipher the molecular dynamics of newly modified and functional insulin analog. A comparative analysis of H/D dynamics demonstrated that the modified insulin exchanges deuterium atoms faster and more extensively than the intact insulin aspart. Additionally, we present new insights derived from our 2.5 Å resolution X-ray crystal structure of modified hexamer insulin analog at ambient temperature. Furthermore, we obtained a distinctive side-chain conformation of the Asn3 residue on the B chain (AsnB3) by operating a comparative analysis with a previously available cryogenic rapid-acting insulin structure (PDB_ID: 4GBN). The experimental conclusions have demonstrated compatibility with modified insulin’s distinct cellular activity, comparably to aspart. Additionally, the hybrid structural approach combined with computational analysis employed in this study provides novel insight into the structural dynamics of newly modified and functional insulin vs insulin aspart monomeric entities. It allows further molecular understanding of intermolecular interrelations driving dissociation kinetics and, therefore, a fast action mechanism.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Calcium Gradient-Doped LiNi 0.5 Mn 1.5 O 4 Cathode for Long Cycle Life Lithium-Ion Batteries

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) has attracted considerable attention as a cathode material for next-generation lithium-ion batteries due to its high operating voltage and intrinsically fast lithium-ion diffusion kinetics. However, the practical implementation of LNMO remains limited by its rapid capacity decay, primarily associated with bulk structural instability and parasitic interfacial reactions. To address these issues, we innovatively introduced calcium (Ca) as a dopant to enhance both the oxygen framework and surface stabilities of the LNMO crystal through gradient doping. Observations from the electronic microscopies, X-ray diffraction, and the elemental analysis confirmed that Ca is preferentially enriched at the particle surface, and a disordered crystal phase is preserved in the bulk in the gradient-doped LNMO cathodes. As cathodes in LIBs, the Ca gradient-doped (Ca gr) LNMO materials delivered formation capacities of ∼126−130 mAh/g and exhibited Coulombic efficiencies of 88−95%, which are consistently higher than those of the uniform-doped samples at the same doping level and undoped sample. Especially, the Ca gr 0.05 LNMO cathode demonstrated significantly improved rate capability with ∼113 mAh/g preserved at 10 C, while ∼92 mAh/g and ∼110 mAh/g for undoped and Ca uniform 0.05 LNMO, respectively, and excellent cycling stability, retaining ∼124.1 mAh/g (∼96.3% capacity retention) after 500 cycles. The analysis of cyclic voltammetry, differential capacity, and electrochemical impedance revealed that the excellent electrochemical performance is attributed to the structural and morphological advantages of gradient-doped LNMO cathodes with a disordered bulk structure for fast Li + diffusion and a Ca-enriched surface for minimizing the Mn dissolution.

25 ENERGY STORAGE↗
DOE OSTI2021

A Platform-Independent X-ray Diffraction Diagnostic for Phase Transition Kinetics in Traditional and Synthetic Microstructure Materials (LDRD Project 213088 Final Report)

Pulsed-power generators using the magnetic loading technique are able to produce well-controlled continuous ramp compression of condensed matter for high-pressure equation-of-state studies. X-ray diffraction (XRD) data from dynamically compressed samples provide direct measurements of the elastic compression of the crystal lattice, onset of plastic flow, strength-strain rate dependence, structural phase transitions, and density of crystal defects such as dislocations. Here, we present a cost effective, compact X-ray source for XRD measurements on pulsed-power-driven ramp-loaded samples. This combination of magnetically-driven ramp compression of materials with single, short-pulse XRD diagnostic will be a powerful capability for the dynamic materials community. The success in fielding this new XRD diagnostic dramatically improves our predictive capability and understanding of rate-dependent behavior at or near phase transition. As Sandia plans the next-generation pulse-power driver platform, a key element needed to deliver new state-of-the-art experiments will be having the necessary diagnostic tools to probe new regimes and phenomena. These diagnostics need to be as versatile, compact, and portable as they are powerful. The development of a platform-independent XRD diagnostic gives Sandia researchers a new window to study the microstructure and phase dynamics of materials under load. This project has paved the way for phase transition research in a variety of materials with mission interest.

36 MATERIALS SCIENCE↗
DOE OSTI2025

In-situ probing of the Fischer-Tropsch reaction on Co single crystal surfaces up to 1 bar

The surface chemistry of the Fischer-Tropsch catalytic reaction over Co has still several unknows. Here, we report an in-situ X-ray photoelectron spectroscopy study of Co$(0001)$ and Co$(10\bar{1}4)$, and in-situ high energy surface X-ray diffraction of Co$(0001)$ during the Fischer-Tropsch reaction at 0.15 bar - 1 bar and 406 K - 548 K in a H 2 /CO gas mixture. We find that these Co surfaces remain metallic under all conditions and that the coverage of chemisorbed species ranges from 0.4–1.7 monolayers depending on pressure and temperature. The adsorbates include CO on-top, C/-C x H y and various longer hydrocarbon molecules, indicating a rate-limiting direct CO dissociation pathway and that only hydrocarbon species participate in the chain growth. The accumulation of hydrocarbon species points to the termination step being rate-limiting also. Furthermore, we demonstrate that the intermediate surface species are highly dynamic, appearing and disappearing with time delays after rapid changes in the reactants’ composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A micromirror array with annular partitioning for high-speed random-access axial focusing

Dynamic axial focusing functionality has recently experienced widespread incorporation in microscopy, augmented/virtual reality (AR/VR), adaptive optics and material processing. However, the limitations of existing varifocal tools continue to beset the performance capabilities and operating overhead of the optical systems that mobilize such functionality. The varifocal tools that are the least burdensome to operate (e.g. liquid crystal, elastomeric or optofluidic lenses) suffer from low (≈100 Hz) refresh rates. Conversely, the fastest devices sacrifice either critical capabilities such as their dwelling capacity (e.g. acoustic gradient lenses or monolithic micromechanical mirrors) or low operating overhead (e.g. deformable mirrors). Here, we present a general-purpose random-access axial focusing device that bridges these previously conflicting features of high speed, dwelling capacity and lightweight drive by employing low-rigidity micromirrors that exploit the robustness of defocusing phase profiles. Geometrically, the device consists of an 8.2 mm diameter array of piston-motion and 48-μm-pitch micromirror pixels that provide 2π phase shifting for wavelengths shorter than 1100 nm with 10–90% settling in 64.8 μs (i.e., 15.44 kHz refresh rate). The pixels are electrically partitioned into 32 rings for a driving scheme that enables phase-wrapped operation with circular symmetry and requires <30 V per channel. Optical experiments demonstrated the array’s wide focusing range with a measured ability to target 29 distinct resolvable depth planes. Overall, the features of the proposed array offer the potential for compact, straightforward methods of tackling bottlenecked applications, including high-throughput single-cell targeting in neurobiology and the delivery of dense 3D visual information in AR/VR.

42 ENGINEERING↗
DOE OSTI2024

Structure-driven development of a biomimetic rare earth artificial metalloprotein

The 2011 discovery of the first rare earth–dependent enzyme in methylotrophic Methylobacterium extorquens AM1 prompted intensive research toward understanding the unique chemistry at play in these systems. This enzyme, an alcohol dehydrogenase (ADH), features a La 3+ ion closely associated with redox-active coenzyme pyrroloquinoline quinone (PQQ) and is structurally homologous to the Ca 2+ -dependent ADH from the same organism. AM1 also produces a periplasmic PQQ-binding protein, PqqT, which we have now structurally characterized to 1.46-Å resolution by X-ray diffraction. This crystal structure reveals a Lys residue hydrogen-bonded to PQQ at the site analogously occupied by a Lewis acidic cation in ADH. Accordingly, we prepared K 142 A- and K 142 D-PqqT variants to assess the relevance of this site toward metal binding. Isothermal titration calorimetry experiments and titrations monitored by UV–Vis absorption and emission spectroscopies support that K 142 D-PqqT binds tightly (Kd = 0.6 ± 0.2 μM) to La 3+ in the presence of bound PQQ and produces spectral signatures consistent with those of ADH enzymes. These spectral signatures are not observed for WT- or K 142 A-variants or upon addition of Ca 2+ to PQQ ⸦ K 142 D-PqqT. Addition of benzyl alcohol to La 3+ -bound PQQ ⸦ K 142 D-PqqT (but not Ca 2+ -bound PQQ ⸦ K 142 D-PqqT, or La 3+ -bound PQQ ⸦ WT-PqqT) produces spectroscopic changes associated with PQQ reduction, and chemical trapping experiments reveal the production of benzaldehyde, supporting ADH activity. By creating a metal binding site that mimics native ADH enzymes, we present a rare earth-dependent artificial metalloenzyme primed for future mechanistic, biocatalytic, and biosensing applications.

Science & Technology - Other Topics↗
DOE OSTI2024

Efficient crystal structure materials as reactive sorbent for the CO 2 and CH 4 adsorption and storage

The efficient dirubidium cobalt bis(dihydrogendiphosphate) dihydrate compound is successfully synthesized in a solution and used as a reactive sorbent for the CO 2 and CH 4 gases adsorption and storage. A crystal of this Rb 2 Co(H 2 P 2 O 7 ) 2 ·2H 2 O compound has been isolated and characterized by single X-ray diffraction analysis and was found to crystallize in the triclinic system (P$\overline{1}$) with the cell parameters (Å): 6.980(1), 7.370(1), 7.816(1), 81.74(1), 70.35(1), 86.34(1); V = 374.68(9) Å3, Z = 2. The crystal-packing consists of a three-dimensional framework made upon corners and edges sharing of [RbO 7 ], [H 2 P 2 O 7 ] and [CoO 6 ] entities, furthermore linked by a network of H-bonds. The UV–Vis spectroscopy revealed usual transitions between the ground state 4T1g and the upper levels 4T2g, 4A2g and 4T1g (P). Moreover, the CO 2 and CH 4 gases sorption measurements were successfully performed at two different temperatures (25 and 45 °C) and various pressures ranging from vacuum to 50 bar. Our results show that rate of CO 2 and CH 4 capturing was 3.10 mmol/g and 2.35 mmol/g at temperature 25 °C and pressure 50 bar, respectively. This compound showed a clear potential for CO 2 /CH 4 adsorption and storage thereby paving the way towards its exploration and adaptation for capturing and collecting carbon dioxide and greenhouse gases from the air, and their conversion into hydrocarbon fuels using existing mature technologies. We have also conducted density functional theory calculations to study the CO 2 and CH 4 adsorption properties of Rb 2 Co(H 2 P 2 O 7 ) 2 ·2H 2 O. The simulation results show enhanced adsorption of both types of molecules on the surface of the material.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Quantifying Dynamic Signal Spread in Real-Time High-Energy X-ray Diffraction

Abstract Measured intensity in high-energy monochromatic X-ray diffraction (HEXD) experiments provides information regarding the microstructure of the crystalline material under study. The location of intensity on an areal detector is determined by the lattice spacing and orientation of crystals so that changes in the heterogeneity of these quantities are reflected in the spreading of diffraction peaks over time. High temporal resolution of such dynamics can now be experimentally observed using technologies such as the mixed-mode pixel array detector (MM-PAD) which facilitates in situ dynamic HEXD experiments to study plasticity and its underlying mechanisms. In this paper, we define and demonstrate a feature computed directly from such diffraction time series data quantifying signal spread in a manner that is correlated with plastic deformation of the sample. A distinguishing characteristic of the analysis is the capability to describe the evolution from the distinct diffraction peaks of an undeformed alloy sample through to the non-uniform Debye–Scherrer rings developed upon significant plastic deformation. We build on our previous work modeling data using an overcomplete dictionary by treating temporal measurements jointly to improve signal spread recovery. We demonstrate our approach in simulations and on experimental HEXD measurements captured using the MM-PAD. Our method for characterizing the temporal evolution of signal spread is shown to provide an informative means of data analysis that adds to the capabilities of existing methods. Our work draws on ideas from convolutional sparse coding and requires solving a coupled convex optimization problem based on the alternating direction method of multipliers.

Engineering↗
DOE OSTI2021

Modeling of crystallization fouling on a horizontal-tube falling-film evaporator for thermal desalination

Scale formation within horizontal-tube falling-film evaporators is an important issue for thermal desalination, because of the deterioration of heat transfer performance and added maintenance costs. Predicting the fouling process is crucial for desalination plant design, operation, and maintenance. In this paper, a model is developed to predict the crystallization fouling process during seawater falling-film flow over a horizontal tube bundle. The scaling is estimated based on deposition theory, with couple heat transfer including the in-tube steam condensation, conduction through the tube wall and the scale layer, and falling-film evaporation. The spatial and temporal variations of temperature, heat transfer coefficient, and scale thickness are predicted, and the effects of variations in process parameters of steam, feed seawater, and tube properties on the scale thickness, evaporation rate, and heat transfer coefficient for falling-film evaporation are analyzed. Comparisons to existing experimental data show the scaling layer thickness falls in the general range of reported measurements, with a slight overestimation due to neglecting the delay of scaling onset under real conditions. The scale layer thickness increases dramatically as the in-tube steam pressure is increased or the seawater flow rate is decreased. In general, the scaling layer becomes thicker on the lower tubes in the tube bundle, due to the heat and mass transfer of the falling film. The effect of tube material on scaling appears mainly dependent on thermal conductivity; thus, using polymer rather than a stainless steel tube decreases scaling and evaporation rate 96% and 88%, respectively. Finally, this work has potential to guide thermal desalination plant design, material selection, and operating parameter optimization.

42 ENGINEERING↗
DOE OSTI2026

Co-templating of polyoxoniobates and silicate/germanate trimer-rings in crystals and inorganic gels

Polyoxometalate (POM) supramolecular gels are a growing family of materials, both for understanding fundamental self-assembly and fabricating flexible monolithic materials that retain the function of metal oxides. Here, we exploited the pH-dependent speciation of polyoxoniobates (PONbs), targeting the formation of PONb-containing supramolecular gels that contain other low molecular weight components (silicate, germanate, phosphate, and carbonate). The introduction of gaseous CO 2 into aqueous hexaniobate solutions resulted in the formation of both new crystalline phases and highly transparent gels. The crystalline phases, formulated Cs 24 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Si 3 O 9 )]·19.6H 2 O and Cs 21 Na 3 [Nb 7 O 22 (NbO(CO 3 ) 2 ) 9 (Ge 3 O 9 )]·33.6H 2 O are templated by a rare planar [X 3 O 9 ] 6− (X = Si, Ge) ring. Crystalline phases were not obtained with phosphate; instead, the gels contain a mixture of phosphate-centred PONbs and network-forming phosphate. POM speciation within the gels, physical properties, and assembly mechanisms were benchmarked by solution and solid-state nuclear magnetic resonance (NMR) spectroscopy, vibrational spectroscopies, small-angle X-ray scattering (SAXS), and thermogravimetry-mass spectroscopy. Optical analysis and dielectric behavior of the gels confirmed that they are highly transparent ionic and electronic conductors. The alkali and hydroxide concentration controls the formation of crystalline materials or supramolecular gels while maintaining the same network building blocks, providing a rare opportunity to describe the molecular-level structure of inorganic amorphous materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Probing the Framework Metal Dependent Properties of Actinide-Centered Polyoxoalkoxide Sandwich-Type Complexes

Development of a simple and scalable synthesis of (TBA) 3 [W 5 O 18 MoNO] provides for the formation of the mixed-metal lacunary polyoxoalkoxide, (TBA) 2 [W 4 O 13 (OMe) 4 MoNO][Na(MeOH)]. This complex was used to synthesize a series of polyoxoalkoxide sandwich-type complexes with the general formula (TBA) 2 [M{W 4 O 13 (OMe) 4 MoNO} 2 ], where M = Zr(IV), Hf(IV), Th(IV), U(IV), and Np(IV). Compared to the analogous all-molybdenum complexes, the series have drastically different optical and redox properties. The results indicate that framework metal substitution acts as a tool for “orbital engineering”, with Density Functional Theory (DFT) calculations revealing that the major consequence of incorporation of tungsten into the complexes is localization of LUMO and LUMO+1 on the molybdenum centers remaining in the molecule. The change in the distribution of the frontier orbitals translates to discrepancies in the electronic properties of the series. Given the rarity of polyoxometalate complexes featuring a U(V) ion, one electron oxidation of (TBA) 2 [U(IV){W 4 O 13 (OMe) 4 MoNO} 2 ] was pursued. Isolation of the corresponding U(V) centered sandwich-type complex is reported, only the second example of U(V)-polyoxometalate complex described to date.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Phase-field modeling of the interactions between an edge dislocation and an array of obstacles

Obstacles, such as voids and precipitates, are prevalent in crystalline materials. They strengthen crystals by serving as barriers to dislocation glide. Here in this work, we develop a phase-field dislocation dynamics (PFDD) technique for investigating the interactions between dislocations and second-phase obstacles, which can be either voids or precipitates. The PFDD technique is constructed to account for elastic heterogeneity, elastic anisotropy, dissociation of the dislocation, and dislocation transmission across bicrystalline interfaces. Within the framework, we present a model for “pseudo-voids”, which are voids shearable by dislocations, in contrast to unphysical, unshearable voids in conventional phase-field dislocation formulations. We employ the PFDD technique to investigate the in-plane interactions between an edge dislocation and an array of nano-scale obstacles with different spacings. In this application, the interactions take place in glide planes of either a face-centered cubic (FCC) Cu or a body-centered cubic (BCC) Nb matrix, while the precipitates have a Cu 1-x Nb x composition, with x varying from 0.1 to 0.9. Our atomistic simulations find that the alloy precipitates can have an FCC, an amorphous, or a BCC phase, depending on the compositional ratio between Cu and Nb, i.e., value of x. Among all types of obstacles, the critical stresses for dislocation bypass are the highest for unshearable amorphous precipitates, followed by shearable crystalline precipitates, and then the pseudo-voids.

42 ENGINEERING↗
DOE OSTI2020

Unraveling the nature of Fe-doping mediated inter- and intra-chain interactions in Ca 3 Co 2 O 6

The structural and magnetic properties of quasi-one-dimensional (1D) spin-chain compounds Ca 3 Co 2-x Fe x O 6 (x = 0, 0.1, 0.2 and 0.3) synthesized by a sol-gel method have been systematically studied by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), neutron powder diffraction (NPD), dc and ac magnetization measurements. The samples adopt a rhombohedral crystal structure with the space group R-3c in a temperature range of 5–100 K. Fe ions are found to locate at the trigonal prism Co2 crystallographic sites. Fe doping converts some of low-spin Co 3+ ions at Co1 octahedral sites into Co 2+ ions. For the high-temperature paramagnetic phase, the Curie paramagnetic temperature θp changes its sign from positive to negative at x = 0.2, implying that the dominant magnetic interaction is driven from ferromagnetic (FM) to antiferromagnetic (AFM) upon Fe substitution. A partial low-spin to high-spin state crossover of the Co1 ions is observed at high Fe-doping level x = 0.3. All the samples exhibit a long-range spin-density wave (SDW) AFM ordering below TN, followed by a spin-glass-like transition at Tf. These low-temperature magnetic phases were significantly suppressed upon Fe doping. The Fe substitution in Ca 3 Co 2-x Fe x O 6 weakened both intrachain and interchain magnetic interactions, caused by enhanced magnetic disorder due to the different magnetic characters of Ising Co and Heisenberg Fe spins.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Decoupling indentation size and strain rate effects during nanoindentation: A case study in tungsten

Materials indented at small scales may simultaneously exhibit indentation size and strain rate effects which complicate the identification of the mechanisms that control deformation and strength. Here, in this work, we explore the possibility that indentation size and rate effects in some materials can be decoupled in a simple way. Nanoindentation tests with various load-time histories were carried out to measure the hardness of a tungsten single crystal over a wide range of indentation depths (~500–3600 nm) and indentation strain rates (~5 ×10 –5 –2 ×10 –1 s –1 ). Under these conditions, this material exhibits significant indentation size and rate effects, but the size effect is, to a good approximation, independent of strain rate. It is shown that this behavior can be understood by the Nix-Gao model for the indentation size effect modified to include the effects of a strain rate dependent friction stress. As a consequence, the size and rate dependencies of the hardness can be expressed as the sum of two independent terms: H($\dot{ε}$ i , h c )=H f ($\dot{ε}$ i ) + (H 0 – H f ) $\sqrt{1+ \frac{h^*}{h_c}}$, where H($\dot{ε}$ i , h c ) is the hardness at given indentation strain rate ($\dot{ε}$ i ) and contact depth (h c ), H f ($\dot{ε}$ i ) is the hardness contributed by the rate dependent friction stress, and (H 0 – H f ) and h* are size and rate independent constants that follow from the Nix-Gao analysis. This formula, together with an expression for the rate dependence of H f , was successfully applied to decouple the indentation size and rate effects observed in tungsten. In addition, the physics underlying the rate independence of indentation size effect is discussed, which provides guidance for application of the proposed approach to other materials.

42 ENGINEERING↗
DOE OSTI2026

Topochemical Oxidation of Ruddlesden–Popper Nickelates Reveals Distinct Structural Family: Oxygen-Intercalated Layered Perovskites

Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, in this study, we report a new family of layered perovskites realized through topochemical oxidation of La n+1 Ni n O 3n+1+δ (n = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial c-axis expansion─17.8% for La 2 NiO 4+δ (n = 1)─that monotonically decreases with increasing n. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.

Ferenc Segedin, Dan [Harvard Univ., Cambridge, MA ↗
DOE OSTI2025

Controlling solvation in conducting redox polymers for selective electrochemical separation of nitrate from wastewater

Selective capture of nitrate from wastewater is crucial for ensuring safe drinking water and promoting resource circularity. This study investigated alkylated polyaniline redox polymers as highly-selective electrosorbents to address this challenge. By controlling polymer solvation properties through synthetic functionalization, poly(N-methylaniline) (PNMA) achieves a nitrate uptake of up to 1.38 mmol g −1 -polymer and a separation factor of 7 over chloride. Poly(N-butylaniline) (PNBA) further enhances selectivity, achieving a separation factor beyond 14 due to increased hydrophobicity. The mechanisms underlying this selectivity are investigated using ab initio molecular dynamics (AIMD) and in-situ electrochemical quartz crystal microbalance (EQCM) studies, which reveal that hydrophobicity reduces chloride binding. A technoeconomic analysis indicates that methylation on PANI reduces nitrate removal costs by 50% compared to non-functionalized PANI, due to enhanced selectivity and uptake, and decreased energy consumption. PNMA electrodes demonstrate practical nitrate selectivity over 20 versus chloride in real wastewater, while avoiding sulfate binding. This study highlights the potential of controlling solvation at electroactive polymers to enhance nitrate selectivity, offering a promising design path for redox-mediated electrochemical separations.

chemical engineering↗
DOE OSTI2023

A Novel Experimental Approach to Understand the Transport of Nanodrugs

Nanoparticle-based drugs offer attractive advantages like targeted delivery to the diseased site and size and shape-controlled properties. Therefore, understanding the particulate flow of the nanodrugs is important for effective delivery, accurate prediction of required dosage, and developing efficient drug delivery platforms for nanodrugs. In this study, the transport of nanodrugs including flow velocity and deposition is investigated using three model metal oxide nanodrugs of different sizes including iron oxide, zinc oxide, and combined Cu-Zn-Fe oxide synthesized via a modified polyol approach. The hydrodynamic size, size, morphology, chemical composition, crystal phase, and surface functional groups of the water-soluble nanodrugs were characterized via dynamic light scattering, transmission electron microscopy, scanning electron microscopy-energy dispersive X-ray, X-ray diffraction, and fourier transform infrared spectroscopy, respectively. Two different biomimetic flow channels with customized surfaces are developed via 3D printing to experimentally monitor the velocity and deposition of the different nanodrugs. A diffusion dominated mechanism of flow is seen in size ranges 92 nm to 110 nm of the nanodrugs, from the experimental velocity and mass loss profiles. The flow velocity analysis also shows that the transport of nanodrugs is controlled by sedimentation processes in the larger size ranges of 110–302 nm. However, the combined overview from experimental mass loss and velocity trends indicates presence of both diffusive and sedimentation forces in the 110–302 nm size ranges. It is also discovered that the nanodrugs with higher positive surface charges are transported faster through the two test channels, which also leads to lower deposition of these nanodrugs on the walls of the flow channels. The results from this study will be valuable in realizing reliable and cost-effective in vitro experimental approaches that can support in vivo methods to predict the flow of new nanodrugs.

36 MATERIALS SCIENCE↗