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At least 37 records · Page 2

Design Principles for the Synthesis of Self-Pillared ZSM-5 Zeolite Nanosheets

The design of next-generation materials for emerging energy and environmental applications heavily relies on empirical approaches to direct nonclassical nucleation and crystal growth pathways, polymorphism, intercrystalline transformations, and seed-assisted growth processes. A long-standing obstacle to nanoporous materials design is the complexity of their crystallization, which hinders the development of predictive models and/or physical descriptors that can guide their synthesis. In this study, we use a combination of state-of-the-art synthesis, characterization, and computational design to prepare hierarchical MFI-type zeolites, which we couple with benchmark catalytic testing to assess structure-property-performance relationships. These hierarchical materials are intergrowths of two commercially relevant zeolite frameworks, MFI and MEL, prepared as self-pillared pentasil (SPP) zeolites through seed-assisted, organic-free syntheses for which little theoretical guidance existed. Here, by comparing a large library of zeolite seeds with different pore sizes, dimensions, and structural composite building units, we determined the relative impact of seed and silica source selection, among other synthesis variables. Combined experimental and computational studies are used to test several hypotheses in literature to rationalize the choice of seed structure and establish a more robust selection criteria for seed-assisted synthesis of zeolites. Specifically, we show that a data-driven approach to develop structural descriptors correlates to new, facile routes to rationally design SPP zeolites, addressing knowledge gaps in the fundamental understanding of (non)classical crystal growth mechanisms that are characteristic of nanoporous aluminosilicates.

36 MATERIALS SCIENCE

Selectivity mechanisms of ion intercalation in Prussian blue analogs

Prussian blue analogs (PBAs) are a family of materials with facile, reversible, and selective ion transport capability for various ions via electrochemical intercalation, owing to their vacancy structure. The large tunable compositional space of PBAs allows for manipulation of intercalation behavior and selectivity by controlling structural vacancy level through choice of transition metal centers and modifications to the synthesis process. However, a lack of understanding of the mechanisms of ion selectivity hinders the material’s design process. Here, for this work, we investigated the origins of ion selectivity using a model PBA, copper hexacyanoferrate, and focused on eight technologically and biologically prominent ions, for which we determined a sequence of selectivity: Rb + > K + > Na + > Ba 2+ > Sr 2+ ≈ Ca 2+ > Mg 2+ > Li + . We provide electrochemical, structural, and redox evidence of strong correlation between the ion identity, the dominant charge-compensating redox, and preferred occupancy site. Specifically, using synchrotron anomalous X-ray diffraction (AXRD), we reveal that monovalent ions exhibit significant association with the corner sites of the unit cell and iron redox, whereas divalent ions display affinity toward the center site with higher ratios of copper redox. Informed by selectivity results, we applied CuHCFe to Li purification and achieved 99.9% purity. Our findings demonstrate an approach to elucidating ion intercalation behavior in order to distinguish and manipulate material properties to optimize separation performance.

Prussian blue analog

Computer-aided design of stability enhanced nicotinamide cofactor biomimetics for cell-free biocatalysis

Cell-free biocatalysis (CFB) is an efficient and environmentally friendly method to synthesize molecules such as pharmaceuticals, biochemicals, and biofuels through the in vitro use of enzyme cascades. These enzymes often require redox cofactors to drive chemical reactions. Natural redox cofactors (NAD(P)H) are expensive to isolate, motivating synthetic nicotinamide cofactor biomimetics (NCBs) as a cost-effective solution. A select handful of NCBs have been identified as potential NAD(P)H alternatives with comparable or improved redox capabilities, however, they display a tendency to degrade in common buffers. In this study, a library of 132 NCB candidates is systematically generated, over 85% of which have not been characterized in the literature, to expand the diversity of currently explored NCBs. The decomposition mechanism of NCBs in phosphate is evaluated using density functional theory (DFT), revealing protonation at the nicotinamide C5 position as a reporter of cofactor stability. Based on this result, we trained a linear regression model on DFT calculated descriptors to predict NCB stability in phosphate buffer, achieving mean absolute error (MAE) and root mean squared error (RMSE) values within computational accuracy. Analysis of key atomic descriptors and qualitative trends in our dataset informed the design of novel NCB candidates we propose with optimized stability. This work enables researchers to predict the relative stability of NCBs before synthesis, thereby streamlining the process to make CFB more affordable and viable at industry scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Selective Electrochemical End‐Group Removal Enhances Polymer Thermal Stability

Here we introduce an electrochemical strategy for the selective and quantitative removal of thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) or photoiniferter polymerization. Our results indicate that applying a cathodic potential in an undivided cell promotes reductive cleavage of the thiocarbonylthio moiety, generating terminal polymer radicals that are efficiently capped with hydrogen atoms in the presence of benign donors. This transformation proceeds cleanly across diverse polymer backbones and end-group chemistries, including trithiocarbonates and dithiobenzoates, without chain coupling or degradation. Moreover, the applied potential can be tuned to enable chemoselective end-group removal in mixed-polymer systems, a level of control inaccessible by thermal, photochemical, or nucleophilic strategies. Beyond delivering colorless and optically transparent materials, electrochemical end-group removal significantly enhances polymer stability. Poly(methyl methacrylate) subjected to electrochemical end-group removal exhibited a T 95 of 342 °C, exceeding the stabilities of analogous polymers with end groups removed by aminolysis (T 95 = 260 °C) or radical-based methods (T 95 = 299 °C). These findings demonstrate redox-directed post-polymerization modification as a tool for designing robust, transparent, and thermally stable macromolecules and establish electrochemistry as a platform strategy in polymer synthesis and processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Plasma-Assisted Surface Nitridation of Proton Intercalatable WO 3 for Efficient Electrocatalytic Ammonia Synthesis

Electrocatalytic nitrogen reduction (eNRR) offers a green pathway for the production of NH 3 from N 2 and H 2 O under ambient conditions. Transition metal oxynitrides (TMO x N y ) are among the most promising catalysts but face challenges in achieving a high yield and faradaic efficiency (FE). This work develops a hybrid WO x N y /WO 3 catalyst with a unique heterogeneous interfacial complexion (HIC) structure. This design enables in situ generation and delivery of highly active hydrogen atoms (H*) in acidic electrolytes, promoting nitrogen hydrogenation and the formation of nitrogen vacancies (Nv) on the WO x N y surface. This significantly enhances the selectivity of eNRR for NH 3 synthesis while suppressing the hydrogen evolution reaction (HER). A simple two-step fabrication process─microwave hydrothermal growth followed by plasma-assisted surface nitridation─was developed to fabricate the designed catalyst electrode, achieving an NH 3 yield of 3.2 × 10 –10 mol·cm –2 ·s –1 with 40.1% FE, outperforming most TMN/TMO x N y electrocatalysts. Multiple control experiments confirm that the eNRR follows an HIC-enhanced Mars–van Krevelen (MvK) mechanism.

Catalysts

Structure and mechanical properties of grain boundaries in molybdenum disulfide (MoS 2 )

Molybdenum disulfide (MoS 2 ) is a two-dimensional material widely used as a lubricant in many applications involving mechanical loading under a wide range of operating temperatures. Since many synthesis and processing techniques yield MoS 2 in its polycrystalline form, establishing grain boundary (GB) structure–property relations is key to designing MoS 2 microstructures with tailored properties. Here, we employ classical, reactive atomistic simulations to investigate the structure and mechanical behavior of a wide range of GBs in MoS 2 as a function of temperature. Using a bicrystal MoS 2 geometry, we characterize the atomic structure and calculate the energy of several low-angle GBs. Then, we simulate the tensile deformation behavior of MoS 2 bicrystals at several temperatures. Our results reveal that at temperatures above 100 K, the deformation of MoS 2 bicrystals is characterized by the nucleation of shear bands from GBs that grow, with subsequent loading, into the MoS 2 crystals. At low temperatures, the tensile deformation is characterized by the nucleation and propagation of deformation fronts, resulting in altered bond angles and bond lengths. Quantitative analysis reveals a decrease in the ultimate tensile stress and ultimate failure strain of MoS 2 bicrystals with the increase in temperature. Furthermore, our simulations of the mechanical behavior of metastable GBs reveal that the strength and ductility decrease with the increase in energy of these boundary structures. In broad terms, our work provides future avenues to employ GB engineering as a strategy to tailor the properties of MoS 2 microstructures.

Moore, Robert D. [Lehigh Univ., Bethlehem, PA (Uni

FiberFlex: Real-time FPGA-based Intelligent and Distributed Fiber Sensor System for Pedestrian Recognition

In recent years, security monitoring of public places and critical infrastructure has heavily relied on the widespread use of cameras, raising concerns about personal privacy violations. To balance the need for effective security monitoring with the protection of personal privacy, we explore the potential of optical fiber sensors for this application. This article proposes FiberFlex, an intelligent and distributed fiber sensor system. Ultizing Field Programmable Gate Arrays (FPGA) high-level synthesis (HLS) acceleration, FiberFlex offers real-time pedestrian detection by co-designing the entire pipeline of optical signal acquisition, processing, and recognition networks based on the principles of optical fiber sensing. As a promising alternative to traditional camera-based monitoring systems, FiberFlex achieves pedestrian detection by analyzing the vibration patterns caused by pedestrian footsteps, enabling security monitoring while preserving individual privacy. FiberFlex comprises three modules: First , fiber-optic sensing system: A fiber-optic distributed acoustic sensing (DAS) system is built and used to measure the ground vibration waves generated by people walking. Second , algorithms: We first collect the training data by measuring the ground vibration waves, label the data, and use the data to train the neural network models to perform pedestrian recognition. Third , hardware accelerators: We use HLS tools to design hardware modules on FPGA for data collection and pre-processing and integrate them with the downstream neural network accelerators to perform in-line real-time pedestrian detection. The final detection results are sent back from FPGA to the host CPU. We implement our system FiberFlex with the in-house built DAS system and AMD/Xilinx Kintex7 FPGA KC705 board and verify the whole system using the real-world collected data. We conduct recognition tests on five test subjects of varying ages, heights, and weights in a fixed sensing area. Each subject experienced 20 real-time recognition tests using their daily walking habits, and the subjects were given adequate rest between tests. After 100 tests on five test subjects, the overall real-time recognition accuracy exceeded \(88.0\%\) . The whole system uses 55 W of power, 33 W in the optical DAS system and 22 W in the FPGA. Relying on its end-to-end interdisciplinary design, FiberFlex seamlessly combines fiber-optic sensors with FPGA accelerators to enable low-power real-time security monitoring without compromising privacy, making it a valuable addition to the existing security monitoring network. According to FiberFlex, more valuable research can be conducted in the future, such as fall monitoring for the elderly, migration of identification networks between different application scenarios, and improvement of anti-interference performance in more complex environments. In future perception networks, where the “eyes” are not feasible, let’s use fiber optic touch instead.

Distributed

Rigid cationic ligands enable high-efficiency NIR-II photoluminescence in copper( i ) iodide hybrid semiconductors

Near-infrared (NIR) luminescent materials are pivotal for advanced optoelectronic and biomedical applications, yet attaining efficient emission in the NIR-II region (950-1400 nm) remains challenging. Here, we introduce a ligand cationization strategy for designing copper(i) iodide-organic hybrid materials that emit in the NIR-II region (920-1120 nm) with PLQYs up to 8.58%. By incorporating rigid cationic ligands with CuI modules, we synergistically achieve bandgap narrowing (to 1.51 eV) and structural rigidification via ionic-dative bonding, effectively suppressing non-radiative decay while extending emission beyond 1100 nm. Coupled with solution processability-enabled by the successful synthesis of nanometer-sized nanoparticles in various shapes-and excellent thermal stability (≥210 °C), this work establishes ligand cationization as a universal approach for designing efficient NIR-II emitters.

Chen, Jingwen

Next-generation electronics by co-design with chalcogenide materials

As Moore’s law approaches its limits, chalcogenides offer a promising route to next-generation computing and sensing, thanks to their topological, magnetoelectric, excitonic, and spintronic properties. Yet the same traits that make them appealing, e.g., exotic properties at monolayer thickness, clean van der Waals interfaces, and strong many-body effects, also heighten sensitivity to fabrication, hindering translation into scalable devices. Progress is further constrained by fragmented knowledge across synthesis, processing, and integration, and by the lack of systematic links between fabrication parameters and performance metrics. This Perspective examines key obstacles in controlling chalcogenide heterostructures and stresses the need for an integrated co-design framework, uniting materials growth, processing, and device architecture to accelerate practical technologies.

36 MATERIALS SCIENCE

Truncating 2D Framework Materials Down to a Single Pore: Synthetic Approaches and Opportunities

Here, in this Accounts article, we summarize our recent work on truncating conjugated two-dimensional framework materials down to a single pore, or a single macrocycle. Conjugated 2D architectures have emerged as one of the most synthetically adaptable motifs for coupling semiconductivity and porosity in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). However, despite their prevalence, 2D architectures have several limitations. In particular, the strong interlayer π–π stacking can limit both processability and the accessibility of internal active sites. We have found that simple macrocycles preserve key aspects of 2D framework structure and function, including porosity and out-of-plane electrical conductivity, while providing improved processability, surface tunability, and mass transport properties. In this article, we first describe our synthetic approach and general design considerations. Specifically, we show how ditopic analogues of the tritopic ligands commonly found in the synthesis of 2D MOFs and COFs can be used to achieve a diverse library of conjugated macrocycles that resemble fragments of semiconducting frameworks in both form and function. The length of the peripheral side chains, the size of the aromatic core, and the solubility of intermediates are all key variables in favoring selective macrocycle formation over undesired linear polymers and oligomers. Next, we highlight the unique advantages that macrocycles provide, including improved processability, atomically precise surface tunability, and greater active site accessibility. In particular, the identity of the peripheral side chains dramatically impacts both solubility and colloidal stability as well as crystal size and morphology. We further show how the solution processability and nanoscale dimensions of macrocycles can simplify electronic device fabrication and improve electrochemical performance. Finally, we end with a forward-looking discussion on how macrocycles offer a unique bridge between conjugated molecules and extended frameworks, enabling new application areas and fundamental science.

charge transport

A Synthesis Methodology for Intelligent Memory Interfaces in Accelerator Systems

Domain-specific systems improve the performance of a specific set of applications compared to general-purpose processing systems by deploying custom hardware accelerators. These hardware accelerators are generated using high-level synthesis (HLS) tools. The HLS tools enable a comprehensive design space exploration to optimize the compute performance of the generated accelerators. However, they often ignore the challenges of implementing the accelerators in a system-on-chip, particularly how the accelerators access memory. Our work introduces a buffering system design that improves accelerators' memory accesses by intelligently employing burst transactions to prefetch useful data from external memory to on-chip local buffers. Our design is dynamic, parametric, and transparent to the accelerators generated by HLS tools. We derive the buffering system parameters using appropriate compiler-based analysis passes and memory channel latency constraints. The proposed buffering system design results in, on average, 8.8x performance improvements while lowering memory channel utilization on average by 53.2% for a set of PolyBench kernels.

Limaye, Ankur M. (ORCID:0000000194062584)

Synthesis Roadmap for Actinide Chloride Salts

Molten salt reactors (MSRs) are among the main advanced nuclear reactor types at the forefront of development by industry, with the support of the US government, for the next fleet of nuclear reactors to support the demand for energy in the coming decades. MSRs are highly unique because they are cooled and typically also fueled by molten salt. This quality brings about safety benefits such as low-pressure operation and self-stabilization of the neutron flux, operational benefits such as high-temperature operation and the ability for online refueling, and fuel and waste management benefits thanks to the flexibility of post-processing of molten salts and reprocessing options that involve removal of fission products and actinide separation. In fact, domestic deployment of molten salt (or molten salt–cooled) reactors is an approaching reality: a handful of molten salt reactor developers are planning to operate demonstration-scale reactors, as a step toward commercial-scale power reactors, within the decade. For example, Natura Resources received a construction permit in September 2024 for the deployment of MSR-1, which is a graphite-moderated thermal spectrum reactor, at Abilene Christian University. Also, TerraPower, in a collaborative effort with Southern Company and Idaho National Laboratory (INL), received approval from DOE in 2023 to proceed with the construction of the Molten Chloride Reactor Experiment (MCRE), a homogeneous chloride fast reactor at INL, and has begun assembly of system components. There are several other examples of developers at different stages of development of their own unique MSR designs (Jenet et al., 2025). As developers are in the process of obtaining approvals for their designs, deploying demonstration-scale reactors, and planning for their commercial-scale power reactors, there is a critical supply chain need for the synthesis of fuel for these reactors that must be addressed. The challenge generally is three-fold: (1) the quantity of fueled salt needed for these reactors is extraordinarily high (>100s of kilograms), but demonstrations of scaled-up techniques for fueled salt synthesis are significantly more limited than demonstrations of lab-scale syntheses; (2) each developer has a unique reactor design, which means different actinide halide elements in different carrier salts must be synthesized; and (3) there is a need for particularly high-purity salt so as to ensure the long-term operability of these reactors with minimal degradation to salt-wetted components, which necessitates synthesis techniques with high levels of quality control, repeatability, and well-characterized precursor and reactant materials. It is crucial that this supply chain challenge be addressed by demonstrating synthesis techniques that are scalable, de-risked, and well-documented so that these technologies may be adopted and utilized by industry to support the fueling needs of MSRs that are to come online within the next 10 years. With this supply chain challenge clearly defined for the developing MSR industry, it is important to consider that addressing such a challenge is oftentimes complex and context-dependent. There is not necessarily a single synthesis technique that can be scaled up and adopted to address the needs of all MSR developers; the synthesis approach that may be viable for producing a desired fuel salt will be entirely dependent on the exact salt composition needed, the quantity needed, purity needed, the refueling and waste plans, and the availability of a carrier salt for the fuel. Therefore, it is important to consider more broadly what synthesis techniques are available and have been demonstrated to understand the benefits, challenges, and general nuances that should be considered when evaluating a particular route for efficient production of high-purity fuel salts at scale.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Accurate Prediction of pKb in Amines: Validation of the CAM-B3LYP/6-311+G(d,p)/SMD Model

Amines play several key roles in chemistry and biology and are involved in numerous industrial processes, often with significant economic impacts. Recently, amines are also garnering interest as catalysts for polymer synthesis and for CO 2 fixation, incentivizing the need to rapidly design and screen new amino compounds. Hence, developing reliable methods to predict their physicochemical properties, e.g., the base dissociation constant (pKb), is pivotal. Here, a density functional theory (DFT)-based approach was employed to compute the pKb of substituted amines, exploring the impact of several key parameters, including (i) the number of explicit water molecules at the reaction center, (ii) the van der Waals (vdW) surface, and (iii) solvent polarizability. In previous work, it was determined that including two explicit water molecules at the reaction center resulted in highly accurate pKb estimates for primary amines. Here, we find that including a third water molecule at the reaction center is essential for accurate pKb for secondary and tertiary amines. The revised methodology was then applied to a wider selection of amines, obtaining a minimum average error (MAE) < 0.4. In conclusion, this result represents an extension of our “easy-to-use method,” a simple and direct DFT approach exploiting CAM-B3LYP/SMD/6-311G+(d,p) to compute pKb without post facto modifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Manufacturing of Al-Ce/Metal-Matrix-Composites (MMC) for Harsh Environments

An integrated modeling/simulation and experimental approach will be used to design and synthesize Al-Ce/MMC for use in key technologies where improved energy efficiency and performance is harsh environments is required. Modeling and simulation work including thermodynamic modeling, DFT calculations, and continuum modeling of casting processes and mechanical behavior, will be combined with lab-scale synthesis to identify potential matrix and reinforcing phase compositions for large-scale synthesis. The experimental synthesis work will rely on lab-scale casting and gas atomization to identify the optimal matrix compositions for pilot/commercial-scale synthesis is Al-Ce/MMC. Selected Al-Ce/MMC will be synthesized by commercial scale melt processing, powder metallurgy and thermomechanical processing. The corrosion resistance, mechanical properties as a function of temperature, and thermal conductivity of the composites will be characterized to validate target properties are met or exceeded. This work will focus on two selected applications; however, the design framework will have broad applicability for composites for numerous harsh service condition applications. We will have synthesized Al-Ce/MMC that exhibit better performance in harsh environments than currently used materials.

36 MATERIALS SCIENCE

Automation of Nanoparticle Synthesis Processes in a Plasma Environment Using LabVIEW

This work presents an automated control system for the synthesis of nanomaterials by plasma-enhanced chemical vapor deposition (PECVD), implemented using the LabVIEW software environment. The main objective of the study is to develop an integrated hardware-software platform that enables sequential control of the key stages of the PECVD process, including vacuum chamber preparation, pressure monitoring, working gas supply, plasma ignition, power matching, cyclic nanomaterial growth, and optical monitoring of nanoparticles in the plasma environment. The use of LabVIEW made it possible to integrate actuator control, experimental parameter acquisition, and realtime process visualization within a single automated system. The automated cycle begins with evacuation of the reaction chamber to a predefined base pressure. Transition to the next stage is permitted only after the specified pressure threshold has been reached, ensuring reproducible initial conditions for each experiment. The program then controls the supply of the working gas through mass flow controllers (MFCs). In this work, two gas-flow control modes were considered: analog control using a 0-5 V voltage signal and digital communication via RS-232 interface. It was shown that the analog approach requires accurate scaling of the control voltage, since applying 5 V corresponds to full-scale opening of the controller and results in the maximum gas flow. In contrast, the RS232 interface enables the gas flow rate to be specified directly in sccm, improving the accuracy, flexibility, and convenience of gas-environment control. After pressure stabilization, LabVIEW initiates RF plasma ignition and executes the RF matching algorithm aimed at minimizing reflected power and improving the stability of the plasma process. A separate software module implements the cyclic nanomaterial growth mode, in which the plasma-on time, plasma duration, and total number of synthesis cycles are predefined. This approach makes it possible to control material accumulation on the substrate and to correlate the process parameters with the morphological characteristics of the resulting nanostructures. The final module of the system is designed for optical monitoring of the nanoparticle cloud density in dusty plasma. For this purpose, the change in the intensity of laser radiation passing through the plasma region is recorded using a photodetector and a Keithley 2401 measuring unit connected to LabVIEW via RS-232 interface. The difference between the initial and modified optical signal intensity is used as a diagnostic parameter characterizing the formation and temporal evolution of nanoparticles. The developed system demonstrates that LabVIEW can be effectively applied not only for the automation of individual instruments, but also for the implementation of a complete digital control cycle for PECVD-based nanomaterial synthesis.

PECVD