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At least 271 records · Page 15

Theoretical Multinary Perovskite Oxides Dataset

Perovskite oxides (ternary chemical formula ABO3) are a diverse class of materials with applications including heterogeneous catalysis, solid-oxide fuel cells, thermochemical conversion, and oxygen transport membranes. However, their multicomponent chemical space is underexplored due to the immense number of possible compositions. To expand the number of computed compounds we report a dataset of 66,516 theoretical multinary oxides, 59,708 of which are perovskites. First, the AA'BB'O6 compositions were generated in the a-b+a- Glazer tilting mode using the computationally-inexpensive Structure Prediction and Diagnostic Software (SPuDS) program. Next, we optimized these structures with DFT using parameters compatible with the Materials Project (MP) database. Our dataset contains these optimized structures and their formation (ΔHf) and decomposition enthalpies (ΔHd) computed relative to MP tabulated elemental references and competing phases, respectively. This dataset can be mined, used to train machine learning models, and rapidly and systematically expanded by optimizing more SPuDS-generated AA'BB'O6 perovskite structures using MP-compatible DFT calculations

Bare, Zachary↗

Evaluation of Technologies for Destruction of LDR Organics in Hanford Tank Waste

Aqueous Hanford tank wastes contain soluble organics and some tanks contain small amounts (<100 mg/L) of organics that are regulated under the Land Disposal Restrictions (LDR) portions of the Resource Conservation and Recovery Act (RCRA). Most of these organics can be removed by evaporation, but some are not. Methods to destroy/remove organics that are regulated by the LDR section of the RCRA and that are not removed by evaporation may be needed if ambient temperature waste treatment processes are used to immobilize aqueous Hanford tank wastes. To identify viable and compatible organic removal or destruction pretreatment methods an evaluation was performed by a team of researchers. The team utilized a Systems Engineering Approach that examines all aspects of the technology, based on information available in the literature and the experience of the team members. That evaluation led to recommendations by the team to perform testing on technologies to determine efficacy in destroying organics in Hanford tank waste liquids. The primary technologies recommended are chemical oxidants, including permanganate, peroxymonosulfate or peroxydisulfate (PMS/PDS), hydrogen peroxide, and ozone. Ultraviolet light irradiation of the stream with a solid catalyst sorbent is also recommended for testing. A generalized description of the test program is also included.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries

Designing highly conductive and (electro)chemical stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO 2 (-ACl)-A 2 ZrCl 6 (A = Li or Na) that demonstrate improved ionic conductivities at 30 °C, from 0.40 to 1.3 mS cm -1 and from 0.011 to 0.11 mS cm -1 for Li + and Na + , respectively, compared to A 2 ZrCl 6 , and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li 2 O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and 6 Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li 2 ZrCl 6 , the fluorinated ZrO 2 -2Li 2 ZrCl 5 F HNSE shows improved high-voltage stability and interfacial compatibility with Li 6 PS 5 Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li + conductivity. We also report the assembly and testing of a Li-In||LiNi 0.88 Co 0.11 Mn 0.01 O 2 all-solid-state lab-scale cell operating at 30 °C and 70 MPa and capable of delivering a specific discharge of 115 mAh g -1 after almost 2000 cycles at 400 mA g -1 .

36 MATERIALS SCIENCE↗

TeraChem protocol buffers ( TCPB ): Accelerating QM and QM/MM simulations with a client–server model

The routine use of electronic structures in many chemical simulation applications calls for efficient and easy ways to access electronic structure programs. Here, we describe how the graphics processing unit (GPU) accelerated electronic structure program TeraChem can be set up as an electronic structure server, to be easily accessed by third-party client programs. We exploit Google’s protocol buffer framework for data serialization and communication. The client interface, called TeraChem protocol buffers (TCPB), has been designed for ease of use and compatibility with multiple programming languages, such as C++, Fortran, and Python. To demonstrate the ease of coupling third-party programs with electronic structures using TCPB, we have incorporated the TCPB client into Amber for quantum mechanics/molecular mechanics (QM/MM) simulations. The TCPB interface saves time with GPU initialization and I/O operations, achieving a speedup of more than 2× compared to a prior file-based implementation for a QM region with ~250 basis functions. We demonstrate the practical application of TCPB by computing the free energy profile of p-hydroxybenzylidene-2,3-dimethylimidazolinone (p-HBDI - )—a model chromophore in green fluorescent proteins—on the first excited singlet state using Hamiltonian replica exchange for enhanced sampling. All calculations in this work have been performed with the non-commercial freely-available version of TeraChem, which is sufficient for many QM region sizes in common use.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High‐Performance and Durable Fuel Cells using Co/Sr‐Free Fluorite‐Based Mixed Conducting (Pr,Ce)O 2‐δ Cathode

Abstract A major challenge to overcome in demonstrating solid oxide fuel cells (SOFCs) to be suitable as efficient and environmentally friendly energy conversion devices capable of addressing pressing clean energy and environmental needs is to surmount chemical and thermo‐mechanical instabilities in their operational phase. To date, perovskite‐based mixed conducting cathodes, which include inherent Co and Sr elements for enhanced reactivity and conductivity, have been intensively studied. These Co/Sr‐based oxides, however, exhibit severe thermochemical expansion and suffer from Sr surface segregation, ultimately degrading the electrode performance. Here, high‐performance and durable SOFCs are demonstrated by employing a Co/Sr‐free fluorite‐based mixed conducting (Pr,Ce)O 2‐δ (PCO) cathode eminently compatible with fluorite‐based solid electrolytes. The nanocolumnar PCO electrode developed in this study provides not only a remarkable low level of electrode resistance (e.g., ≈0.05 Ω cm 2 at 600 °C) but also exceptional long‐term stability (e.g., a degradation rate 15 times slower compared to the state‐of‐the‐art La 0.6 Sr 0.4 CoO 3‐δ perovskite). The competitive peak power densities of an anode‐supported single cell with the PCO cathode are also successively achieved, recording a value of 0.92 W cm −2 at 600 °C. These findings herald the development of new Co/Sr‐free electrodes for SOFCs at intermediate temperatures.

30 DIRECT ENERGY CONVERSION↗

Carbon Corrosion in CO2 Electrolysis Systems

Driven by concerns over climate change, interest in CO2 conversion technologies has dramatically increased in recent years. By viewing CO2 as a readily available feedstock, many pathways for the production of carbon-neutral fuels and chemicals become available. In converting CO2, low carbon emitting energy sources must be used to ensure a low carbon footprint of the fuel and chemical products. The low-temperature electrochemical conversion of CO2 is a promising technology and allows for direct integration with renewable electricity sources. The development of low-temperature CO2 electrolysis technologies is informed by both PEM fuel cells and water electrolyzers, both of which are at a higher stage of development. However, CO2 electrolysis operates at a much higher cell voltage (-3V) than other low-temperature electrochemical processes, which can have implications for materials compatibility in the electrolyzer device. Carbon corrosion is of particular concern for the anode of CO2 electrolyzers, as a large driving force for corrosion exists due to the high required cell potentials. In this presentation, recent observations will be shared on carbon corrosion of the anode gas diffusion electrode (GDE) in low-temperature alkaline exchange membrane CO2 electrolysis. Results from ex-situ tests designed to isolate the carbon corrosion process for anode GDEs will be shared. These results will provide guidance on materials selection for CO2 utilization MEAs, which need to have a lifetime of several years to ensure industrial viability.

BIOMASS FUELS↗

Implementation of the Glycolate Destruction Process with Sodium Permanganate in the Defense Waste Processing Facility (DWPF) - 20141

The Savannah River Site (SRS) seeks to replace formic acid with glycolic acid as a chemical reductant in the Defense Waste Processing Facility (DWPF), where borosilicate glass is mixed with high-level radioactive waste, melted at high temperatures, then poured into stainless steel canisters for safe storage. Prior research and development have demonstrated the feasibility and advantages of the new nitric-glycolic acid flowsheet over the current nitric-formic acid flowsheet to chemically adjust the radioactive sludge slurry waste in the Sludge Receipt and Adjustment Tank (SRAT) prior to vitrification. Use of glycolic acid reduces hydrogen and ammonia generation during the reduction process, thus reducing flammability hazards and purge requirements in the DWPF processing vessels. In addition, glycolic acid will support the new Salt Waste Processing Facility (SWPF) by allowing for receipt of higher volumes of waste due to reduction of flammable gases, increased boil-up rates in the vessels, and easing the processing of future sludge batches containing high levels of mercury. However, during DWPF operations, trace amounts of glycolate are anticipated to be entrained in the recycle stream and sent to the Concentration, Storage, and Transfer Facilities (CSTF) via the Recycle Collection Tank (RCT). The RCT receives condensate from the Slurry Mix Evaporator Condensate Tank (SMECT) and Off-gas Condensate Tank (OGCT) that may contain unreacted glycolate. A literature review found the potential for hydrogen generation due to thermolysis of glycolate in caustic CSTF conditions. Savannah River National Laboratory (SRNL) conducted several tests on simulant and radioactive waste from various tanks at SRS and confirmed that glycolate added to waste at concentrations of approximately 1000 mg/L and higher generates hydrogen through thermolysis. There are potential operating scenarios in the future where glycolate concentration could exceed 1000 mg/L in the 2H Evaporator Drop Tank, the highest accumulation point for DWPF organics received via recycle. These findings presented a need to develop another process to mitigate the impact of glycolic acid to the CSTF. Several DWPF compatible options were evaluated for their ability to destroy glycolate in the DWPF recycle stream under various processing conditions, thereby mitigating its introduction to the CSTF. Downselection testing identified sodium permanganate as the most promising and simplest option to oxidize glycolate. It has been demonstrated to be effective in various RCT simulant compositions, operating temperatures, oxidant addition rates, solution pH, and initial glycolate concentrations. A feasibility study identified existing tanks within the facility that could be used for receiving and storing the commercially available sodium permanganate, as well as feeding it to the RCT for processing. The use of existing equipment as well as the ability to purchase the pre-mixed chemical reduces implementation and operational complexity. The downstream impacts of the sodium permanganate reaction were also evaluated and demonstrated to have minimal impact on other chemical species present in the RCT and CSTF, as well as on the materials of construction of the RCT and CSTF vessels and associated piping and instrumentation. Future work is in progress to validate the glycolate destruction process with testing in actual radioactive RCT waste before implementation in DWPF. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Investigating the electronic structure of high explosives with X-ray Raman spectroscopy

Abstract We investigate the sensitivity and potential of a synergistic experiment-theory X-ray Raman spectroscopy (XRS) methodology on revealing and following the static and dynamic electronic structure of high explosive molecular materials. We show that advanced ab-initio theoretical calculations accounting for the core-hole effect based on the Bethe-Salpeter Equation (BSE) approximation are critical for accurately predicting the shape and the energy position of the spectral features of C and N core-level spectra. Moreover, the incident X-ray dose typical XRS experiments require can induce, in certain unstable structures, a prominent radiation damage at room temperature. Upon developing a compatible cryostat module for enabling cryogenic temperatures ( $$\approx$$ ≈ 10 K) we suppress the radiation damage and enable the acquisition of reliable experimental spectra in excellent agreement with the theory. Overall, we demonstrate the high sensitivity of the recently available state-of-the-art X-ray Raman spectroscopy capabilities in characterizing the electronic structure of high explosives. At the same time, the high accuracy of the theoretical approach may enable reliable identification of intermediate structures upon rapid chemical decomposition during detonation. Considering the increasing availability of X-ray free-electron lasers, such a combined experiment-theory approach paves the way for time-resolved dynamic studies of high explosives under detonation conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porosity as a Design Element for Developing Catalytic Molecular Materials for Electrochemical and Photochemical Carbon Dioxide Reduction

The catalytic reduction of carbon dioxide (CO 2 ) using sustainable energy inputs is a promising strategy for upcycling of atmospheric carbon into value-added chemical products. This goal has inspired the development of catalysts for selective and efficient CO 2 conversion using electrochemical and photochemical methods. Among the diverse array of catalyst systems designed for this purpose, two- and three-dimensional platforms that feature porosity offer the potential to combine carbon capture and conversion. Included are covalent organic frameworks (COFs), metal-organic frameworks (MOFs), porous molecular cages, and other hybrid molecular materials developed to increase active site exposure, stability, and water compatibility while maintaining precise molecular tunability. This mini-review showcases catalysts for the CO 2 reduction reaction (CO 2 RR) that incorporate well-defined molecular elements integrated into porous materials structures. Selected examples provide insights into how different approaches to this overall design strategy can augment their electrocatalytic and/or photocatalytic CO 2 reduction activity. This article is protected by copyright. All rights reserved.

36 MATERIALS SCIENCE↗

Foundry-compatible high-resolution patterning of vertically phase-separated semiconducting films for ultraflexible organic electronics

Solution processability of polymer semiconductors becomes an unfavorable factor during the fabrication of pixelated films since the underlying layer is vulnerable to subsequent solvent exposure. A foundry-compatible patterning process must meet requirements including high-throughput and high-resolution patternability, broad generality, ambient processability, environmentally benign solvents, and, minimal device performance degradation. However, known methodologies can only meet very few of these requirements. Here, a facile photolithographic approach is demonstrated for foundry-compatible high-resolution patterning of known p- and n-type semiconducting polymers. This process involves crosslinking a vertically phase-separated blend of the semiconducting polymer and a UV photocurable additive, and enables ambient processable photopatterning at resolutions as high as 0.5 μm in only three steps with environmentally benign solvents. The patterned semiconducting films can be integrated into thin-film transistors having excellent transport characteristics, low off-currents, and high thermal (up to 175 °C) and chemical (24 h immersion in chloroform) stability. Moreover, these patterned organic structures can also be integrated on 1.5 μm-thick parylene substrates to yield highly flexible (1 mm radius) and mechanically robust (5,000 bending cycles) thin-film transistors.

36 MATERIALS SCIENCE↗

A variable X-ray chopper system for phase-sensitive detection in synchrotron X-ray scanning tunneling microscopy

An ultra-high-vacuum compatible X-ray chopper system has been designed, constructed and integrated into the XTIP beamline at the Advanced Photon Source at Argonne National Laboratory. The XTIP beamline can operate at soft X-ray energies from 400 eV to 1900 eV while providing a focused beam down to about 10 µm × 10 µm into the synchrotron X-ray scanning tunneling microscopy (SX-STM) endstation instrument. The X-ray chopper is a critical component for separating topographic information from chemical information in SX-STM through phase-sensitive current detection. Depending on the experimental needs, the modulation frequency can be controlled from 100 Hz to 10 kHz. In addition, the chopper system is fully bakeable and can achieve a base pressure of 10 -10 mbar. Facilities for active water cooling have been designed, but passive cooling through copper braids has been shown to be sufficient at standard chopping frequencies. Using an Fe/Al 2 O 3 /CoAl(111) sample, the separation of the SX-STM current into a chemical component and a stable feedback signal is demonstrated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

BETO 2021 Peer Review - Catalytic Upgrading of Pyrolysis Vapors 2.3.1.314

Catalytic fast pyrolysis (CFP) is a versatile pathway for the direct liquefaction of biomass and waste carbon sources to generate a stabilized bio-oil intermediate that can be further processed into renewable fuels, chemicals, and materials. The objective of this project is advance the CFP state-of-technology through integrated catalyst and process development, expand market responsiveness by creating routes to novel co-products, and provide experimental data to inform process modelling and scale-up activities. Research advancements over the past two years include reducing analytical uncertainty by achieving 100 ± 1% carbon balances during reaction testing with woody biomass, improving process efficiency by achieving a 4x increase in catalyst cycle length, demonstrating compatibility with waste feedstocks, and confirming process durability for 100+ reaction cycles. Additionally, this project supported a comprehensive pathway review to evaluate scale-up needs. This review resulted in the early identification of technical risks and informed proactive planning for the BETO 2022 Verification. Other impacts from this project include generation of broadly enabling scientific knowledge (14 publications/18 presentations since 2019), engagement with industry partners (e.g., Johnson Matthey and ExxonMobil), and identification of a promising pathway to market that addresses emerging demands for biogenic refinery feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Substrate effects on phase formation and interfacial stability in superconducting vanadium silicide thin films

Thin films of vanadium silicide (V-silicide) in the A15 cubic phase (V 3 Si) are promising for superconducting quantum devices due to their high transition temperature and potential compatibility with scalable semiconductor fabrication. However, solid-phase synthesis often yields secondary silicide phases that degrade performance. Here, in this study, we investigate the influence of substrate properties using two silicon-on-insulator architectures: one with a polycrystalline HfO 2 buried layer (group A) and the other with amorphous SiO 2 (group B). Both systems exhibit superconductivity consistent with V 3 Si formation, yet structural analysis reveals mixed-phase films in both cases. Crucially, only group A maintains an atomically sharp and chemically stable interface, a prerequisite for phase purity. Prolonged annealing in group A reduces the unwanted V 5 Si 3 phase but also leads to the emergence of Si-rich VSi 2 , likely due to localized substrate degradation. Preliminary atomic-resolution imaging suggests that HfO 2 crystallinity may promote local phase-selective nucleation. These findings highlight the importance of substrate design in promoting phase control and maintaining interfacial integrity in superconducting silicides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Chemical Imaging for In Situ Detection and Discrimination of Aquatic Toxins Targeting Voltage Gated Sodium Channels

Biologically derived neurotoxins from cyanobacteria and algae impact environmental resources in addition to being considered a potential biological threat to human and animal health. Activity based assays are essential to detecting and responding to toxic neurotoxin events either naturally occurring or deliberate. Two toxins of interest include saxitoxin and brevetoxin. These toxins bind to and alter the function of voltage-gated sodium channels (NaV channels) which are essential for generating cell membrane action potential. We report the development and refinement of a System for Analysis at Liquid Vacuum Interface (SALVI) to assess the functional activity of saxitoxin and brevetoxin. This approach utilizes a vacuum-compatible microfluidic reactor that permits analysis at the liquid vacuum interface of human derived cells with a neurotoxin of interest in a biologically relevant environment.

54 ENVIRONMENTAL SCIENCES↗

Crystal and Electronic Structures of A 2 NaIO 6 Periodate Double Perovskites (A = Sr, Ca, Ba): Candidate Wasteforms for I-129 Immobilization

The synthesis, structure, and thermal stability of the periodate double perovskites A 2 NaIO 6 (A= Ba, Sr, Ca) were investigated in the context of potential application for the immobilization of radioiodine. A combination of X-ray diffraction and neutron diffraction, Raman spectroscopy, and DFT simulations were applied to determine accurate crystal structures of these compounds and understand their relative stability. The compounds were found to exhibit rock-salt ordering of Na and I on the perovskite B-site; Ba 2 NaIO 6 was found to adopt the Fm- 3 m aristotype structure, whereas Sr 2 NaIO 6 and Ca 2 NaIO 6 adopt the P 2 1 / n hettotype structure, characterized by cooperative octahedral tilting. DFT simulations determined the Fm- 3 m and P 2 1 / n structures of Ba 2 NaIO 6 to be energetically degenerate at room temperature, whereas diffraction and spectroscopy data evidence only the presence of the Fm- 3 m phase at room temperature, which may imply an incipient phase transition for this compound. The periodate double perovskites were found to exhibit remarkable thermal stability, with Ba 2 NaIO 6 only decomposing above 1050 °C in air, which is apparently the highest recorded decomposition temperature so far recorded for any iodine bearing compound. As such, these compounds offer some potential for application in the immobilization of iodine-129, from nuclear fuel reprocessing, with an iodine incorporation rate of 25–40 wt%. The synthesis of these compounds, elaborated here, is also compatible with both current conventional and future advanced processes for iodine recovery from the dissolver off-gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rechargeable Manganese Dioxide||Hard Carbon Lithium Batteries in an Ether Electrolyte

Earth-abundant, cost-effective electrode materials are essential for sustainable rechargeable batteries and global decarbonization. Manganese dioxide (MnO 2 ) and hard carbon both exhibit high structural and chemical tunability, making them excellent electrode candidates for batteries. Herein, we elucidate the impact of electrolytes on the cycling performance of commercial electrolytic manganese dioxide in Li chemistry. We leverage synchrotron X-ray analysis to discern the chemical state and local structural characteristics of Mn during cycling, as well as to quantify the Mn deposition on the counter electrode. By using an ether-based electrolyte instead of conventional carbonate electrolytes, we circumvent the formation of a surface Mn(II)-layer and Mn dissolution from Li x MnO 2 . Consequently, we achieved an impressive ~100% capacity retention for MnO 2 after 300 cycles at C/3. To create a lithium metal-lean full cell, we introduce hard carbon as the anode which is compatible with ether-based electrolytes. Commercial hard carbon delivers a specific capacity of ~230 mAh g -1 at 0.1 A g -1 without plateau, indicating a surface-adsorption mechanism. The resulting manganese dioxide||hard carbon full cell exhibits stable cycling and high Coulombic efficiency. Our research provides a promising solution to develop cost-effective, scalable, and safe energy storage solutions using widely available manganese oxide and hard carbon materials.

25 ENERGY STORAGE↗

Fiber Sorbents – A Versatile Platform for Sorption-Based Gas Separations

Increasing demand for high-purity fine chemicals and a drive for process intensification of large-scale separations have driven significant work on the development of highly engineered porous materials with promise for sorption-based separations. While sorptive separations in porous materials offer energy-efficient alternatives to longstanding thermal-based methods, the particulate nature of many of these sorbents has sometimes limited their large-scale deployment in high-throughput applications such as gas separations, for which the necessary high feed flow rates and gas velocities accrue prohibitive operational costs. These processability limitations have been historically addressed through powder shaping methods aimed at the fabrication of structured sorbent contactors based on pellets, beads or monoliths, commonly obtained as extrudates. These structures overcome limitations such as elevated pressure drops commonly recorded across powder adsorption beds but often accrue thermal limitations arising from elevated particle density and aggregation, which ultimately cap their maximum separation performance. Furthermore, the harsh mechanical strain to which powder particles are subjected during contactor fabrication, in the form of extrusion/compression forces, can result in partial pore occlusion and framework degradation, further limiting their performance. Here, we present the development of porous fiber sorbents as an alternative sorbent contactor design capable of addressing sorbent processability limitations while enabling an array of performance-maximizing heat integration capabilities. This new sorbent form factor leverages pre-existing know-how from hollow fiber spinning to produce fiber-shaped sorbent contactors through the phase inversion of known polymers in a process known as dry-jet/wet quenching. The process of phase inversion allows microporous sorbent particles to be latched onto a macroporous polymer matrix under mild processing conditions, thus making it compatible with soft porous materials prone to amorphization under traditional pelletization conditions. Sorbent fibers can be created with different geometries through control of the spinning apparatus and process, offering the possibility to produce monolithic and hollow fibers alike, the latter of which can be integrated with thermalization fluid flows. In this Account, we summarize our progress in the field of fiber sorbents from both design and application standpoints. We further guide the reader through the evolution of this field from the early inceptive work on zeolite hollow fibers to recent developments on MOF fibers. We highlight the versatile nature of fiber sorbents, both from the composition, fabrication and structure points of view, and further demonstrate how fiber sorbents offer alternative paths in tackling new and challenging chemical separation challenges like direct air capture (DAC), with a final perspective on the future of the field.

36 MATERIALS SCIENCE↗