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129 records · Page 3

Rinse-Free, Sodium-Efficient Synthesis of O3-Type Layered Oxide Materials Enabled by Acetate Precursors

Sodium-ion batteries (SIBs) are a sustainable alternative to lithium-ion systems for global electrification, with O3-type layered oxide cathodes offering high specific capacity and feasibility of scalable synthesis. Industrial co-precipitation synthesis of these cathodes typically uses transition metal sulfates, requiring extensive water rinsing to remove Na 2 SO 4 impurities, a process that consumes significant water and risks residual inactive phases if incomplete. Here, this work introduces a rinse-free, resource-efficient approach using metal acetate precursors. Residual sodium acetate in non-rinsed precursors decomposes during sintering to generate Na 2 CO 3 in situ, partially substituting an external sodium resource (e.g., NaOH and Na 2 CO 3 ) and reducing its consumption by ∼18–20%. Phase-pure O3-Na 1.0 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (NFM111) cathodes synthesized via this method exhibit microstructure and electrochemical performance comparable to rinsed sulfate-derived counterparts, with initial capacities of 141 mAh g −1 at C/20 (7.5 mA g −1 ). By eliminating rinsing and minimizing sodium reagent use, this acetate-based route enhances sustainability and scalability of layered oxide production for SIBs.

acetate vs. sulfate

N-Doped Graphene (N-G)/MOF(ZIF-8)-Based/Derived Materials for Electrochemical Energy Applications: Synthesis, Characteristics, and Functionality

In recent years, graphene-type materials originating from metal–organic frameworks (MOFs) or integrated with MOFs have exhibited notable performances across various applications. However, a comprehensive understanding of these complex materials and their functionalities remains obscure. While some studies have reviewed graphene/MOF composites from different perspectives, due to their structural–functional intricacies, it is crucial to conduct more in-depth reviews focusing on specific sets of graphene/MOF composites designed for particular applications. In this review, we thoroughly investigate the syntheses, characteristics, and performances of N-G/MOF(ZIF-8)-based/derived materials employed in electrochemical energy conversion and storage systems. Special attention is given to realizing their fundamental functionalities. The discussions are divided into three segments based on the application of N-G/ZIF-8-based/derived materials as electrode materials for batteries, electrodes for electrochemical capacitors, and electrocatalysts. As electrodes for batteries, N-G/MOF(ZIF-8) materials can mitigate issues like an electrode volume expansion for Li-ion batteries and the ‘shuttle effect’ for Li-S batteries. As electrodes for electrochemical capacitors, these materials can considerably improve the ion transfer rate and electronic conductivity, thereby enhancing the specific capacitance while maintaining the structural stability. Also, it was observed that these materials could occasionally outperform standard platinum-based catalysts for the electrochemical oxygen reduction reaction (ORR). The reported electrochemical performances and structural parameters of these materials were carefully tabulated in uniform units and scales. Through a critical analysis of the present synthesis trends, characteristics, and functionalities of these materials, specific aspects were identified that required further exploration to fully utilize their inherent capabilities.

Electrochemistry

Thin Film Synthesis of SrZn2P2 with SrI2 Post-Annealing for Enhanced Crystallinity and Optoelectronic Quality

Ternary Zintl phosphides are promising light-absorbing semiconductors for thin-film optoelectronic applications, but strategies for controlling their microstructure and optoelectronic quality remain underexplored. Here, we report the synthesis of phase-pure SrZn2P2 thin films using radio-frequency co-sputtering in a PH3 + Ar atmosphere and investigate the impact of post-growth processing on their structural and optical properties. Grazing-incidence X-ray scattering and Raman spectroscopy confirm the formation of crystalline SrZn2P2 films over a finite compositional window. Optical measurements reveal clear absorption near the direct-band-gap energy (~1.8 eV) and near-band-edge photoluminescence. Further, we have studied the effects of chemically compatible halide-assisted annealing. It is found that SrI2 treatments lead to pronounced grain growth and reduced diffraction peak broadening while preserving phase purity, in contrast to rapid thermal or forming-gas annealing. Notably, annealing with SrI2 at 450 degrees C significantly enhances both the intensity and spatial uniformity of the photoluminescence, thus connecting the observed microstructural consolidation with improved radiative recombination. Our study demonstrates that halide-assisted annealing provides an effective pathway for microstructural control in SrZn2P2 thin films and highlights a generalizable processing strategy for advancing Zintl phosphide semiconductors toward optoelectronic applications.

14 SOLAR ENERGY

Monolayer Films of Binary Metal Oxide Nanoparticles for Carbon Nanotube Synthesis

Binary metal oxide nanoparticles (biMO-NPs) combining transition and main-group metals with well-organized atomic architectures have unique potential as robust and economical heterogeneous catalysts. Herein, metal oxide nanoparticles (CoAlxOy) using cobalt and aluminum were synthesized, and their structure, morphology, and chemical composition were investigated using various characterization techniques. The biMO-NPs, which had a Gaussian-type size distribution (∼6 nm), were assembled on plain silicon substrates modified chemically with linker molecules bearing suitable end groups. Surface analysis revealed an ordered, uniform, close-packed arrangement of biMO-NPs forming a monolayer architecture with nanoscale thickness (∼12 nm), high surface uniformity, and negligible defects. The nanoparticle monolayer film (NP-MF) was employed as a catalyst to grow carbon nanotube (CNT) forests via the thermal chemical vapor deposition (CVD) method, similar to those grown from catalyst thin films deposited by physical vapor deposition. Structural characterization confirmed the growth of a dense, uniform, high-quality vertically aligned carbon nanotube (VA-CNT) forest with a length of ∼125 µm, which is comparable to the VA-CNTs grown from expensive thin films. Thus, CNT growth was successfully catalyzed by the biMO-NPs, highlighting a simple and inexpensive alternative for catalyst deposition. In this innovative wet-chemistry approach, the catalyst and catalyst support are combined within a single nanoparticle before NP-MF assembly. Interestingly, this approach provides a scalable and cost-effective pathway for CNT growth, eliminating the need for expensive thin deposition techniques.

Regmi, Bishow [University of Cincinnati]

Improved Protein Semi-Synthesis Enables Biophysical Studies of Thioamide Destabilization of β-Sheet Interactions

Abstract Thioamides are natural post-translational modifications of the peptide backbone and can be introduced synthetically to probe protein folding or functionalize peptides for translational applications. In this work, we demonstrate that thioamide-containing peptides with C-terminal thioesters can be efficiently generated using Knorr pyrazole activation and used in subsequent native chemical ligation reactions to generate thioamide-containing proteins. We compare this method to acyl azide activation and find that both routes provide similar yields. We also investigate ultrasound-mediated desulfurization of the ligation site cysteine for potential advantages over chemical radical initiators. Scaling up our syntheses allows us to study thioamide perturbations to the β-sheet region of the B1 domain of protein G (GB1) as well as β-strand interactions in amyloid fibrils of the Parkinson’s disease protein α-synuclein. In both contexts, we observe dramatic destabilization of the β-sheet networks, manifested in decreased GB1 thermal stability and altered folding and slowed aggregation of α-synuclein. These findings illustrate the impact that a single atom substitution can have on cooperative hydrogen-bonding networks and prompt future study of both systems.

Yanagawa, Evan S. K. [University of Pennsylvania ,

Electron-Deficient Phenazines: Synthesis, Structures, Redox, and Optoelectronic Properties in the Gas Phase, in Solution, and in the Solid State

High-temperature gas-phase reactions of 1,4-C4F8I2 with phenazine (PHNZ) afforded new thermally- and air-stable derivatives with cyclo-C4F8 substituents, viz. 1,2-PHNZ(C4F8), 2,3-PHNZ(C4F8), 1,2:6,7-PHNZ(C4F8)2, 1,2:7,8-PHNZ(C4F8)2, and 1,2:8,9-PHNZ(C4F8)2. Reactions in the presence of Cu powder resulted in reductive-defluorination/aromatization of some of the cyclo-C4F8 substituents to produce 2,3-PHNZ(C4F4), 2,3-PHNZ(C4HF3), and 1,2:6,7-PHNZ(C4F8)(C4F4), which are formally tri- or tetrafluoro derivatives of benzo[a]phenazine. Single-crystal X-ray diffraction structures of these compounds demonstrate the planarity of 2,3-PHNZ(C4F4) and 2,3-PHNZ(C4HF3) and ordered p-stacking in 1,2-PHNZ(C4HF3), 1,2-PHNZ(C4F4), 1,2-PHNZ(C4F8), and 2,3-PHNZ(C4F8). Low-temperature gas-phase photoelectron spectra of the PHNZ(C4F8)1,2 compounds show that they are strong electron acceptors, with the three PHNZ(C4F8)2 isomers having electron affinities exceeding that of C60. Cyclic voltammetry in acetonitrile show that the five PHNZ(C4F8)1,2 compounds exhibit reversible one-electron reductions with large positive shifts in their reduction potentials relative to unsubstituted PHNZ. Spectroelectrochemical absorption and EPR spectra of PHNZ(C4F8)1,2- • anion radicals and extensive DFT calculations revealed the significant role that the different substitution patterns have on determining the optoelectronic properties of the PHNZ(C4F8)1,2 derivatives and PHNZ(C4F8)1,2- • anion radicals. Time-resolved microwave conductivity measurements and photoluminescence spectra of blends of the PHNZ(C4F8)1,2 derivatives with the donor poly(3-hexylthiophene) (P3HT) were recorded to assess the possible use of the new compounds in optoelectronic devices.

Balser, Sebastian

U.S. Pacific Coast Workshop Report on Preconstruction Research Recommendations (U.S. Offshore Wind Synthesis of Environmental Effects Research (SEER) Project)

In May 2022, the U.S. Offshore Wind Synthesis of Environmental Effects Research (SEER) project team hosted a stakeholder workshop focused on preconstruction (baseline) research needs for potential floating offshore wind (OSW) energy development on the U.S. Pacific Coast, including California, Oregon, and Washington. Prior to the workshop, the SEER team developed a set of initial synthesized research recommendations that were identified based on a review of relevant, publicly available resources and with advisory group input. The workshop covered three marine life breakout groups on subsequent days to discuss research recommendations related to 1) marine mammals and sea turtles, 2) fish and invertebrates, and 3) birds and bats. As part of the workshop, over a hundred participants from the public and private sectors provided feedback on various aspects of the initial research recommendations, including associated data and knowledge gaps, benefits/limitations of available methods and technologies, and technological advancements or infrastructure needed to address the recommendation. Approximately 1,000 total comments were received on the workshop MURAL boards and were synthesized in this report. Based on workshop feedback, SEER developed a final database of over 500 specific research recommendations based on more than 40 resources. In Fall 2022, the full database and a tool with updated synthesized research recommendations were disseminated on Tethys (https://tethys.pnnl.gov) to assist with informing future funding opportunities and research programming. There is a continued need to improve awareness of the potential environmental effects, monitoring technologies, and management strategies for floating OSW energy development on the U.S. Pacific Coast. Coordination of these activities will require the sustained involvement of multiple stakeholders from across sectors. Beyond the baseline considerations discussed in this workshop, future state-of-the-science activities should be planned to consider research needs across wind energy life cycle phases for all relevant wildlife taxa and associated habitat and ecosystem processes.

17 WIND ENERGY

NASA Weather Balloon Demonstration of an Additively Manufactured Antenna

Additive manufacturing (AM) enables low-cost, lightweight, and geometrically flexible antennas for rapid deployment missions. This work reports a left-hand circularly polarized magneto-electric dipole printed on a Radix dielectric with inkjet silver metallization and demonstrated as a process replacement for NASA weather-balloon RF hardware. By combining substrate fabrication and metallization, AM provides value for unrecoverable or field-replaceable systems. A physics based verification workflow links AM-specific material behavior to electromagnetic performance and yields bounded total, radiation, and mismatch efficiencies. Standard surface-impedance and roughness models failed to reproduce the frequency-dependent radiation loss observed in printed inks, underscoring the need for AM-specific conductor parameterization. Mission testing confirmed TDRSS link closure from NASA’s Columbia Scientific Balloon Facility and validated a repeatable print–measure–fly workflow for bounding RF performance and qualifying AM antennas for field use.

Peter Moschetti

NASA Weather Balloon Demonstration of an Additively Manufactured Antenna

Additive manufacturing (AM) enables low-cost, lightweight, and geometrically flexible antennas for rapid deployment missions. This work reports a left-hand circularly polarized magneto-electric dipole printed on a Radix dielectric with inkjet silver metallization and demonstrated as a process replacement for NASA weather-balloon RF hardware. By combining substrate fabrication and metallization, AM provides value for unrecoverable or field-replaceable systems. A physics based verification workflow links AM-specific material behavior to electromagnetic performance and yields bounded total, radiation, and mismatch efficiencies. Standard surface-impedance and roughness models failed to reproduce the frequency-dependent radiation loss observed in printed inks, underscoring the need for AM-specific conductor parameterization. Mission testing confirmed TDRSS link closure from NASA’s Columbia Scientific Balloon Facility and validated a repeatable print–measure–fly workflow for bounding RF performance and qualifying AM antennas for field use.

Peter Moschetti

High Pressure Synthesis of Ultrasmall Nanodiamonds with Nitrogen Vacancy Centers

C–H terminated nanometer scale diamonds ( d = 1 to 15 nm) are synthesized from 1-fluoroadamantane at high pressure (6–8 GPa) and high temperature (500–1500 °C) in a multianvil press. High resolution transmission electron microscopy, X-ray diffraction, Raman, diffuse reflectance Fourier transform infrared, and X-ray absorption spectroscopies demonstrate the excellent crystallinity and atomically flat C–H terminated surfaces of nanodiamonds with (111) and (110) facets. The importance of hydrogen to the synthesis of nanodiamond and its faceting is discussed. Following vacancy generation, annealing and oxidation of the nanodiamonds, optically detected magnetic resonance and electron spin resonance coherence times ( T 2 = 0.9 and 2.1 μs) of nitrogen vacancy (NV) centers are measured. Finally, the obtained T 2 values are equivalent to the shallow NV centers (depth <10 nm) in bulk diamond crystals and larger nanocrystals prepared by mechanical milling.

36 MATERIALS SCIENCE

Synthesis‐Related Nanoscale Defects in Mo‐Based Janus Monolayers Revealed by Cross‐Correlated AFM and TERS Imaging

2D Janus transition metal dichalcogenides (TMDs) are promising candidates for various applications including non-linear optics, energy harvesting, and catalysis. These materials are usually synthesized via chemical conversion of pristine TMDs. Nanometer-scale characterization of the obtained Janus materials’ morphology and local composition is crucial for both the synthesis optimization and the future device applications. In this work, we present the results of cross-correlated atomic force microscopy (AFM) and tip-enhanced Raman spectroscopy (TERS) study of Janus monolayers synthesized by the hydrogen plasma-assisted chemical conversion of MoSe 2 and MoS 2 . We demonstrate that the choice of both the growth substrate and the starting TMD influences the residual strain, thereby shaping the nanoscale morphology of the resulting Janus material. Furthermore, by employing TERS imaging, we show the presence of nanoscale islands (≈20 nm across) of MoSe 2 - ${\mathrm{Mo}}_{{\mathrm{Se}}}^{\mathrm{S}}$ (MoS 2 -${\mathrm{Mo}}_{\mathrm{S}}^{{\mathrm{Se}}}$) vertical heterostructures originating from the bilayer nanoislands in the precursor monolayer crystals. The understanding of the origins of nanoscale defects in Janus TMDs revealed in this study can help with further optimization of the Janus conversion process towards uniform and wrinkle-/crack-free Janus materials. Moreover, this work shows that cross-correlated AFM and TERS imaging is a powerful and accessible method for studying nanoscale composition and defects in Janus TMD monolayers.

2D materials

Manipulating Na/TM Ratio‐Driven Structural Heterogeneity of O3‐NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Cathode for High‐Voltage Sodium‐Ion Batteries

The stability of O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 under high-voltage cycling is dictated by how synthesis encodes lattice strain and redox heterogeneity. Here, in this study, the role of Na:TM stoichiometry is systematically resolved by tuning the NaOH:precursor ratio during solid-state synthesis. The stoichiometric condition (Na:TM = 1.00) yields minimized microstrain, enabling uniform O3–P3 phase evolution and homogeneous multi-metal redox with preserved octahedral symmetry. In contrast, Na-excess compositions inherit disordered intermediates and heterogeneous distortion fields that trigger abrupt multiphase transitions and promote localized charge redistribution. In situ XRD captures the divergence in phase-transition pathways, TXM resolves particle-level redox heterogeneity, and XANES corroborates a stronger and more reversible Fe redox contribution at stoichiometry, shifting to diminished Fe participation and spatially inhomogeneous redox at higher Na content. These results establish Na:TM stoichiometry as a critical synthesis parameter controlling both structural coherence and redox stability. Electrochemically, the stoichiometric composition exhibits smooth voltage profiles with minimal polarization growth and retains nearly 80% of its initial capacity after 100 cycles even at an extended 4.2 V cutoff, whereas Na-excess compositions show significantly reduced initial coulombic efficiency and rapid voltage fade. Precise stoichiometric tuning provides a scalable route to defect-suppressed O3 frameworks, enabling structurally resilient, high-voltage sodium-layered cathodes.

36 MATERIALS SCIENCE

NASA’s Electric Propulsion Development Activities for Space Nuclear Propulsion Applications

Given increased worldwide support for advanced nuclear technology for terrestrial applications, there is a renewed interest in the possibility of nuclear-reactor-powered spacecraft. NASA continues investing in the technology areas necessary to support NASA’s future scientific and exploration goals. One of those technologies areas is electric propulsion, a highly efficient means for in-space propulsion that increases fuel economy by ionizing and accelerating an onboard propellant using spacecraft electrical power. The current NASA portfolio of electric propulsion investments in support of space nuclear applications focuses on a range of future applications with total system power levels of 50 kilowatts to multimegawatt. These investments support a fast-paced incremental rate for technology development advancement to support these applications. Systems at the 50-kilowatt power level can be accomplished today with existing technology and systems at the multimegawatt level will require further technology developments over the coming decade. Propulsion systems based an array of multiple Hall thrusters have been identified the most likely technology option for the near-term applications and systems utilizing lithium-fueled magneto-plasma-dynamic thrusters have been identified as the most promising alternative technology option for the far-term applications at very high-power levels.

Electric Propulsion

NASA’s Electric Propulsion Development Activities for Space Nuclear Propulsion Applications

Given increased worldwide support for advanced nuclear technology for terrestrial applications, there is a renewed interest in the possibility of nuclear-reactor-powered spacecraft. NASA continues investing in the technology areas necessary to support NASA’s future scientific and exploration goals. One of those technologies areas is electric propulsion, a highly efficient means for in-space propulsion that increases fuel economy by ionizing and accelerating an onboard propellant using spacecraft electrical power. The current NASA portfolio of electric propulsion investments in support of space nuclear applications focuses on a range of future applications with total system power levels of 50 kilowatts to multimegawatt. These investments support a fast-paced incremental rate for technology development advancement to support these applications. Systems at the 50-kilowatt power level can be accomplished today with existing technology and systems at the multimegawatt level will require further technology developments over the coming decade. Propulsion systems based an array of multiple Hall thrusters have been identified the most likely technology option for the near-term applications and systems utilizing lithium-fueled magneto-plasma-dynamic thrusters have been identified as the most promising alternative technology option for the far-term applications at very high-power levels.

Electric propulsion

Pivotal role of organic adsorbates for the creation of catalytic sites during dry reforming of methane

Inadvertent factors can sometimes be crucial for synthesis of catalysts. The use of polyalcohols is common in the synthesis of heterogeneous catalysts. Interactions between alcohols and heterogeneous catalysts have been shown to induce surface reconstructions that greatly impact catalytic performance. Thus, traces of these alcohol functionalities on the as-synthesized catalysts, combined with heat treatment, could be critical in the generation of catalytic sites. Here, we show that during the synthesis of a Ni–Mo/MgO catalyst using a polyol process, residual ethylene glycol (EG) on the surface plays a significant role in the generation of catalytic sites for dry reforming of methane (DRM). The as-synthesized catalyst presents dispersed cationic Ni. Under DRM reaction conditions, the presence of EG, and H2 generated in situ, promote the generation of co-localized Ni–Mo nanoparticles (NPs). Greater amount of EG in the as-synthesized catalyst prevented sintering, leading to better catalyst stability and higher rates. If the residual EG remaining post-synthesis is removed through calcination, before conducting DRM, NiO NPs are formed and the material is completely inactive for catalyzing the reaction. When using a different support, denoted MgO*, EG also proved indispensable to generate active sites, although Ni–Mo co-localization was not evident, and a combination of DRM-related species was needed to activate the catalyst, not just H2. This work systematically uncovers how the interactions between organic adsorbates, the supported metals and the catalyst support dictate the creation of catalytic active sites.

Polo Garzon, Felipe [ORNL] (ORCID:0000000265076183

Using scalable computer vision to automate high-throughput semiconductor characterization

Abstract High-throughput materials synthesis methods, crucial for discovering novel functional materials, face a bottleneck in property characterization. These high-throughput synthesis tools produce 10 4 samples per hour using ink-based deposition while most characterization methods are either slow (conventional rates of 10 1 samples per hour) or rigid (e.g., designed for standard thin films), resulting in a bottleneck. To address this, we propose automated characterization (autocharacterization) tools that leverage adaptive computer vision for an 85x faster throughput compared to non-automated workflows. Our tools include a generalizable composition mapping tool and two scalable autocharacterization algorithms that: (1) autonomously compute the band gaps of 200 compositions in 6 minutes, and (2) autonomously compute the environmental stability of 200 compositions in 20 minutes, achieving 98.5% and 96.9% accuracy, respectively, when benchmarked against domain expert manual evaluation. These tools, demonstrated on the formamidinium (FA) and methylammonium (MA) mixed-cation perovskite system FA 1−x MA x PbI 3 , 0 ≤ x ≤ 1, significantly accelerate the characterization process, synchronizing it closer to the rate of high-throughput synthesis.

Science & Technology - Other Topics

Excitons in van der Waals magnetic materials

Two-dimensional magnetic semiconductors provide a unique platform where long-range magnetic order coexists with strongly bound excitons. Because excitonic states and magnetic moments originate from the same electronic orbitals and couple via intrinsic exchange interactions, optical excitations in these systems exhibit pronounced sensitivity to magnetic order. Recent experiments show unusually strong magneto-optical responses and direct exciton–magnon coupling, establishing new routes for controlling light–matter interactions with spin degrees of freedom. Here, this Review surveys key developments, focusing on representative material systems, experimental signatures, and theoretical frameworks used to describe these phenomena. We conclude with perspectives on how this rapidly evolving field could enable next-generation optoelectronic and quantum technologies leveraging the coupled dynamics of light, charge and spin.

36 MATERIALS SCIENCE