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At least 415 records · Page 23

Dilute Alloys Based on Au, Ag, or Cu for Efficient Catalysis: From Synthesis to Active Sites

The development of new catalyst materials for energy-efficient chemical synthesis is critical as over 80% of industrial processes rely on catalysts, with many of the most energy-intensive processes specifically using heterogeneous catalysis. Catalytic performance is a complex interplay of phenomena involving temperature, pressure, gas composition, surface composition and structure over multiple length and time scales. In response to this complexity, the integrated approach to heterogeneous dilute-alloy catalysis reviewed here brings together materials synthesis, mechanistic surface chemistry, reaction kinetics, in-situ and operando characterization, and theoretical calculations in a coordinated effort to develop design principles to predict and improve catalytic selectivity. Dilute alloy catalysts—in which isolated atoms or small ensembles of the minority metal on the host metal lead to enhanced reactivity while retaining selectivity—are particularly promising as selective catalysts. Several dilute alloy materials using Au, Ag and Cu as the majority host element, including more recently introduced support-free nanoporous metals and oxide-supported nanoparticle "raspberry colloid templated (RCT)" materials, are reviewed for selective oxidation and hydrogenation reactions. Progress in understanding how such dilute alloy catalysts can be used to enhance selectivity of key synthetic reactions is reviewed, including quantitative scaling from model studies to catalytic conditions. The dynamic evolution of catalyst structure and composition studied in surface science and catalytic conditions and their relationship to catalytic function are also discussed, followed by advanced characterization and theoretical modeling that have been developed to determine the distribution of minority metal atoms at or near the surface. Furthermore, the integrated approach demonstrates the success of bridging the divide between fundamental knowledge and design of catalytic processes in complex catalytic systems, which can accelerate the development of new and efficient catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intrinsically Conductive {pi}‑d Conjugated Layers with Co–N4 Active Sites for Efficient Nitrate Electrocatalysis and Zinc-Nitrate Batteries

Electrochemical synthesis of ammonia from nitrate has been extensively investigated as a potential alternative to the energy-intensive Haber-Bosch process. This approach not only operates under ambient conditions but also simultaneously removes nitrate contaminants while producing ammonia as a value-added product. However, the ongoing quest lies in designing an efficient electrocatalyst that achieves a high ammonia yield rate, high selectivity, and long-term stability. Herein, we report the outstanding performance of a Co–N4 coordinated π-d layered Co3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) in nitrate electrocatalysis. The unique combination of abundant Co–N4 active sites and superior electrical conductivity enables significant electrocatalytic activity, delivering a maximum ammonia yield rate of 56.8 mg cm–2 h–1 at −0.8 V vs RHE and a Faradaic efficiency of ∼91% at −0.4 V vs RHE. Mechanistic analysis reveals that alkaline conditions accelerate water dissociation to generate adsorbed hydrogen intermediates (H*), which are utilized by Co–N4 sites to drive the stepwise hydrogenation of nitrate to ammonia while suppressing competing hydrogen evolution reaction (HER) pathways. Furthermore, integration of this catalyst into a zinc-nitrate battery resulted in a maximum power density of 5.3 mW cm–2 and an open-circuit potential of ∼1.45 V. These results highlight the potential of π-d conjugated Co–N4 materials as an efficient catalyst for both environmental remediation and energy conversion.

Namvar, shahrirar↗

Printing thermoelectric inks toward next-generation energy and thermal devices

The ability of thermoelectric (TE) materials to convert thermal energy to electricity and vice versa highlights them as a promising candidate for sustainable energy applications. Despite considerable increases in the figure of merit zT of thermoelectric materials in the past two decades, there is still a prominent need to develop scalable synthesis and flexible manufacturing processes to convert high-efficiency materials into high-performance devices. Scalable printing techniques provide a versatile solution to not only fabricate both inorganic and organic TE materials with fine control over the compositions and microstructures, but also manufacture thermoelectric devices with optimized geometric and structural designs that lead to improved efficiency and system-level performances. In this review, we aim to provide a comprehensive framework of printing thermoelectric materials and devices by including recent breakthroughs and relevant discussions on TE materials chemistry, ink formulation, flexible or conformable device design, and processing strategies, with an emphasis on additive manufacturing techniques. Additionally, we review recent innovations in the flexible, conformal, and stretchable device architectures and highlight state-of-the-art applications of these TE devices in energy harvesting and thermal management. Perspectives of emerging research opportunities and future directions are also discussed. While this review centers on thermoelectrics, the fundamental ink chemistry and printing processes possess the potential for applications to a broad range of energy, thermal and electronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Langevin dynamics for “noisy” forces

Efficient Boltzmann-sampling using first-principles methods is challenging for extended systems due to the steep scaling of electronic structure methods with the system size. Additionally, stochastic approaches provide a gentler system-size dependency at the cost of introducing “noisy” forces, which could limit the efficiency of the sampling. When the forces are deterministic, the first-order Langevin dynamics (FOLD) offers efficient sampling by combining a well-chosen preconditioning matrix S with a time-step-bias-mitigating propagator [G. Mazzola and S. Sorella, Phys. Rev. Lett. 118, 015703 (2017)]. However, when forces are noisy, S is set equal to the force-covariance matrix, a procedure that severely limits the efficiency and the stability of the sampling. Here, we develop a new, general, optimal, and stable sampling approach for FOLD under noisy forces. We apply it for silicon nanocrystals treated with stochastic density functional theory and show efficiency improvements by an order-of-magnitude.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multifunctional copper single-atom electrocatalyst aerogel for smart sensing and producing ammonia from nitrate

Despite modern chemistry’s success in providing affordable fertilizers for feeding the population and supporting the ammonia industry, ineffective nitrogen management has led to pollution of water resources and air, contributing to climate change. Here, we report a multifunctional copper single-atom electrocatalyst-based aerogel (Cu SAA) that integrates the multiscale structure of coordinated single-atomic sites and 3D channel frameworks. The Cu SAA demonstrates an impressive faradaic efficiency of 87% for NH 3 synthesis, as well as remarkable sensing performance with detection limits of 0.15 ppm for NO 3 − and 1.19 ppm for NH 4 + . These multifunctional features enable precise control and conversion of nitrate to ammonia in the catalytic process, facilitating accurate regulation of the ammonium and nitrate ratios in fertilizers. We thus designed the Cu SAA into a smart and sustainable fertilizing system (SSFS), a prototype device for on-site automatic recycling of nutrients with precisely controlled nitrate/ammonium concentrations. The SSFS represents a forward step toward sustainable nutrient/waste recycling, thus permitting efficient nitrogen utilization of crops and mitigating pollutant emissions. This contribution exemplifies how electrocatalysis and nanotechnology can be potentially leveraged to enable sustainable agriculture.

Science & Technology - Other Topics↗

Mars Science Laboratory CHIMRA: A Device for Processing Powdered Martian Samples

The CHIMRA is an extraterrestrial sample acquisition and processing device for the Mars Science Laboratory that emphasizes robustness and adaptability through design configuration. This work reviews the guidelines utilized to invent the initial CHIMRA and the strategy employed in advancing the design; these principles will be discussed in relation to both the final CHIMRA design and similar future devices. The computational synthesis necessary to mature a boxed-in impact-generating mechanism will be presented alongside a detailed mechanism description. Results from the development testing required to advance the design for a highly-loaded, long-life and high-speed bearing application will be presented. Lessons learned during the assembly and testing of this subsystem as well as results and lessons from the sample-handling development test program will be reviewed.

Sunshine, Daniel↗

Metallic Powder Core Tubular Wire (PCTW) Development for Additive Manufacturing

NASA Langley Research Center (LaRC) in Hampton, VA, and the Center for Welding, Joining, and Coating Research (CWJCR) in the Department of Metallurgical and Materials Engineering at the Colorado School of Mines (CSM) in Golden, CO, have collaborated for nearly fifteen years to develop metallic powder core tubular wire (PCTW) feedstock for additive manufacturing (AM) using electron beam deposition. The motivation for this development was to offset dealloying observed during deposition of titanium and aluminum alloy solid wire feedstock in the LaRC electron beam freeform fabrication (EBF3) system and to explore novel alloy compositions by tailoring the powder fill. EBF3 is a fusion-based AM process that is performed under vacuum and is consequently prone to vaporization loss of low vapor pressure alloying elements. Research spanning four graduate student research projects succeeded in developing the basic methodology to fabricate PCTW, the mass balance equations used to define the powder fill, microstructure control through particulate inoculation, and the feasibility of producing metal matrix composite materials. Metallic PCTW is comprised of a thin foil sheath wrapped around a powder blend. Fabrication of PCTW at CSM was accomplished using a tubular wire mill system to first bend a flat strip into a u-shaped cross section, deposit a powder fill, create a lap joint to seal the wire, and draw to final diameter. Powder management systems were developed to ensure uniform mixing of powder constituents and identify feed rates for optimum fill ratios. Processing parameters were successfully developed for titanium and aluminum alloy sheaths to account for material work hardening during drawing. Mass balance equations were developed to account for compositional contributions of the sheath and powder fill. PCTW composition can be adjusted through selection of the sheath or powder materials. PCTWs were successfully developed to offset Al loss in deposits of Ti-6-4 and Mg loss in Al 6061, resulting in deposits that were within the composition limits for each material. Ti-6-4 deposits were fabricated using PCTW comprised of commercially pure (CP) titanium sheath and a fill of pre-alloyed Ti-6-4 powder with additions of elemental Al and V powders. Additions of both elements were required to account for the CP Ti from the sheath, and Al was further enhanced to offset documented losses in EBF3 deposits. For Al 6061 deposits, composition was modulated through the choice of sheath material. The PCTW was made using an Al 5052 sheath to supplement Mg content and a fill composition of pre-alloyed 6061 powder with additions of Si and Cu.The slower solidification rate of the EBF3 process compared with laser powder bed fusion processes can lead to coarse-grained microstructures and mechanical property anisotropy. EBF3deposits of Ti-6-4 exhibited large epitaxially grown β grains, which result in degraded mechanical properties in the deposition direction. Microstructure refinement was achieved through a combination of electron beam modulation and the use of a PCTW designed for Ti-6-4 deposits and modified by the addition of powder made from Fe and B. Resulting deposits exhibited reductions in β grain size, α phase colony intercept length and lath width, and an increased volume fraction of β phase. The mechanism of microstructure refinement was related to precipitation of boride particles. Hardness testing confirmed that mechanical property anisotropy was reduced and an overall increase in hardness was achieved.Metal matrix composite (MMC) materials offer strength and stiffness benefits over unreinforced materials. Two methods were investigated using PCTW technology for producing Al 6061 basedMMC materials; the direct addition of SiC reinforcing particles and the in-situ generation of reinforcements through reaction synthesis of precursor powders. Al 6061 based MMCs reinforced with SiC exhibited particle clustering and formation of aluminum carbides during deposition. The application of a Ni coating to the SiC particles prior to incorporation into the powder fill eliminated aluminum carbide formation and aided particle distribution during deposition. Modulation of beam focus and power further reduced aluminum carbide formation and aided particle distribution. In reaction synthesis, precursor additions undergo an exothermic reaction during deposition to form new ceramic products, generally of finer scale than the initial precursor components. The product phases provide reinforcement in the MMC and act as nucleation sites during solidification, resulting in grain refinement, improved mechanical properties, and reduced susceptibility to solidification cracking. Higher tensile strength and stiffness were demonstrated in Al 6061 based MMCs with 2 vol% reinforcement. These combined research efforts demonstrate the potential of PCTW technology for customizing of alloy composition and achieving microstructure control. A manufacturing process for titanium- and aluminum-based PCTWs was developed based on iterative design, theoretical calculations, and empirical data. PCTW technology successfully mitigated Al loss from Ti-6-4 and Mg loss in Al 6061, resulted in grain refinement in Ti-6-4, and demonstrated fabrication of Al based MMCs

Marcia S Domack↗

Processing and properties of PSZT 95/5 ceramics with varying Ti and Nb substitution

Niobium doped lead-tin-zirconate-titanate ceramics near the PZT 95/5 orthorhombic AFE – rhombohedral FE morphotropic phase boundary Pb 1-0.5y (Zr 0.865-x Ti x Sn 0.135 ) 1-y Nb y O 3 were prepared according to a 2 2+1 factorial design with x = 0.05, 0.07 and y = 0.0155, 0.0195. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1250°C for 6 hours. All compositions were ~98% dense with no detectable secondary phases by XRD. The ceramics exhibited equiaxed grains with intergranular porosity and grain size was ~5 μm, decreasing with niobium substitution. Compositions exhibited remnant polarization values of ~32 μC/cm 2 , increasing with Ti substitution. Depolarization by the hydrostatic pressure induced FE-AFE phase transition was drastically affected by variation of the Ti and Nb substitution, increasing at a rate of 113 MPa / 1% Ti and 21 MPa / 1% Nb. Total depolarization output was insensitive to the change in Ti and Nb substitution, ~32.8 μC/cm 2 for the PSZT ceramics. The R3c-R3m and R3m-Pm3m phase transition temperatures on heating ranged from 90 to 105°C and 183 to 191°C, respectively. Ti substitution stabilized the R3c and R3m phases to higher temperatures, while Nb substitution stabilized the Pm3m phase to lower temperatures. Thermal hysteresis of the phase transitions was also observed in the ceramics, with transition temperature on cooling being as much as 10°C lower.

36 MATERIALS SCIENCE↗

Quantum Search Compiler (Qsearch) v2.0

Quantum Gate Synthesis is the process of taking a desired quantum gate operation, in this case specified as a unitary matrix, and decomposing it into a list of operations that can actually be performed on a quantum computer. Qsearch is an implementation of a quantum synthesis algorithm based on combining A* search with numerical optimization. It is designed to minimize CNOT count at the expense of having a long runtime. It produces particularly efficient quantum circuits in terms of CNOT count, up until about 4 qubits. It is generally impractical to run Qsearch on circuits with more than 4 qubits, but it can be used as a subroutine in algorithms designed to work with these larger circuits. Qsearch takes the form of a Python package, taking advantage of Numpy and Scipy, with part of the package written in Rust and taking advantage of OpenBLAS, NLOPT, and Google Ceres for faster runtime.

Lancu, Costin↗

Sustainable chemistry with plasmonic photocatalysts

There is a pressing global need to increase the use of renewable energy sources and limit greenhouse gas emissions. Towards this goal, highly efficient and molecularly selective chemical processes that operate under mild conditions are critical. Plasmonic photocatalysis uses optically resonant metallic nanoparticles and their resulting plasmonic, electronic, and phononic light-matter interactions to drive chemical reactions. The promise of simultaneous high-efficiency and product-selective reactions with plasmon photocatalysis provides a compelling opportunity to rethink how chemistry is achieved. Plasmonic nanoparticles serve as nanoscale ‘antennas’ that enable strong light–matter interactions, surpassing the light-harvesting capabilities one would expect purely from their size. Complex composite structures, combining engineered light harvesters with more chemically active components, are a focal point of current research endeavors. In this review, we provide an overview of recent advances in plasmonic catalysis. We start with a discussion of the relevant mechanisms in photochemical transformations and explain hot-carrier generation and distributions from several ubiquitous plasmonic antennae. Then we highlight three important types of catalytic processes for sustainable chemistry: ammonia synthesis, hydrogen production and CO 2 reduction. To help elucidate the reaction mechanism, both state-of-art electromagnetic calculations and quantum mechanistic calculations are discussed. This review provides insights to better understand the mechanism of plasmonic photocatalysis with a variety of metallic and composite nanostructures toward designing and controlling improved platforms for green chemistry in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ADS-1 - A new general-purpose optimization program

Today, numerous programs are available which may be coupled with finite element analysis or other analysis techniques to perform the optimization function in the solution of structural synthesis problems. However, most of these codes include only one or two algorithms and many have not been tested on problems of significant size and complexity. There is, therefore, a need for a reliable, general-purpose, publicly available code, containing a variety of modern algorithms for use in structural synthesis as well as general engineering design. The ADS-1 program (Automated Design Synthesis: Version 1) was written in response to this need. The present investigation has the objective to present the capabilities of the ADS program and to demonstrate its application to structural synthesis. The ADS program solves the general nonlinear constrained optimization problem in the standard form. At each level of the optimization process, several options are available.

Vanderplaats, G. N.↗

Plasma-assisted physical vapor deposition surface treatments for tribological control

In any mechanical or engineering system where contacting surfaces are in relative motion, adhesion, wear, and friction affect reliability and performance. With the advancement of space age transportation systems, the tribological requirements have dramatically increased. This is due to the optimized design, precision tolerance requirements, and high reliability expected for solid lubricating films in order to withstand hostile operating conditions (vacuum, high-low temperatures, high loads, and space radiation). For these problem areas the ion-assisted deposition/modification processes (plasma-based and ion beam techniques) offer the greatest potential for the synthesis of thin films and the tailoring of adherence and chemical and structural properties for optimized tribological performance. The present practices and new approaches of applying soft solid lubricant and hard wear resistant films to engineering substrates are reviewed. The ion bombardment treatments have increased film adherence, lowered friction coefficients, and enhanced wear life of the solid lubricating films such as the dichalcogenides (MoS2) and the soft metals (Au, Ag, Pb). Currently, sputtering is the preferred method of applying MoS2 films; and ion plating, the soft metallic films. Ultralow friction coefficients (less than 0.01) were achieved with sputtered MoS2. Further, new diamond-like carbon and BN lubricating films are being developed by using the ion assisted deposition techniques.

Spalvins, Talivaldis↗

Radiation hardened microprocessor for small payloads

The RH-3000 program is developing a rad-hard space qualified 32-bit MIPS R-3000 RISC processor under the Naval Research Lab sponsorship. In addition, under IR&D Harris is developing RHC-3000 for embedded control applications where low cost and radiation tolerance are primary concerns. The development program leverages heavily from commercial development of the MIPS R-3000. The commercial R-3000 has a large installed user base and several foundry partners are currently producing a wide variety of R-3000 derivative products. One of the MIPS derivative products, the LR33000 from LSI Logic, was used as the basis for the design of the RH-3000 chipset. The RH-3000 chipset consists of three core chips and two support chips. The core chips include the CPU, which is the R-3000 integer unit and the FPA/MD chip pair, which performs the R-3010 floating point functions. The two support whips contain all the support functions required for fault tolerance support, real-time support, memory management, timers, and other functions. The Harris development effort had first passed silicon success in June, 1992 with the first rad-hard 32-bit RH-3000 CPU chip. The CPU device is 30 kgates, has a 508 mil by 503 mil die size and is fabricated at Harris Semiconductor on the rad-hard CMOS Silicon on Sapphire (SOS) process. The CPU device successfully passed tesing against 600,000 test vectors derived directly on the LSI/MIPS test suite and has been operational as a single board computer running C code for the past year. In addition, the RH-3000 program has developed the methodology for converting commercially developed designs utilizing logic synthesis techniques based on a combination of VHDK and schematic data bases.

Shah, Ravi↗

Network science can improve the sustainable development of solar energy

Abstract The recent emergence of agrivoltaic and ecovoltaic approaches to ground-mounted photovoltaic (PV) energy provides a much-needed alternative to the environmentally disruptive practices employed in utility-scale solar development. Research on such land-sharing approaches has grown rapidly, with an emphasis on characterizing how PV arrays impact ecosystem processes and agricultural productivity. Although these studies have done well to quantify a variety of dual-use solar practices by employing site-specific sampling designs, this approach has limited our ability to synthesize results across sites, regions, and globally. We call for a network science approach for improved cross-site synthesis of dual-use solar research. We contend that a common approach for data collection and synthesis will facilitate a more rigorous investigation of the agricultural and ecological impacts of PV development across space and over time. The products of this scientifically informed approach can be directly applied to improve sustainable land management.

Bacon, Taylor (ORCID:0009000518578569)↗

Integrated Capture and Conversion of CO 2 to Methanol (ICCCM) Process Technology - CRADA 449 (Final Report)

The goal of this project is to develop a prototype system that integrates the capture and catalytic hydrogenation of CO 2 into methanol in the same solvent. Ultimately, this integrated approach could provide a technology with projected reductions to capital and operating costs by at least 20% relative to a benchmark methanol synthesis via gas-phase CO 2 hydrogenation. There were five primary objectives for the project: 1. Optimize the selections of both the catalysts and the CO 2 capture solvents to achieve high conversion (>80%) and high selectivity (>90%) toward methanol in the targeted processing ranges (100-180°C, 1-60 bar). 2. Design a reactor system that provides a fixed catalyst surface area and high-efficiency heat exchange to assure compact modular processing. 3. Build and test a reactor system and demonstrate in a bench scale continuous flow system, and use the operating data to refine the comparison to existing conversion technologies. 4. Refine techno economic (TEA) and Tech-to-Market (TTM) analyses using the experimental data obtained from the bench-scale system. 5. Use the experimental data and TEA/TTM projections to develop a conceptual design for a pre-commercial system that targets a specific market opportunity.

09 BIOMASS FUELS↗

Understanding the Molecular‐level Interactions Between Ionic Liquids and Molecular Species to Design and Develop Novel Solvent Systems for Environmental and Energy Applications (DOE-EPSCoR – DE‐SC0020282 Final Technical Report)

The central theme of the work is to develop an understanding of the molecular-level interactions between ionic liquids and molecular species that govern a specific set of separations (aliphatic/aromatic, Topic I), reactions (SNAr, high-temp reactions, Topic II) and polymer (ultrahigh performance polymers, Topic III) synthesis processes through the synergistic application of synthesis, characterization and simulation. Understanding these interactions will provide significant insight into how to optimize these and other processes that are influenced by these interactions. An important additional goal is to build the collaborative infrastructure to enable the cluster researchers to develop professional relationships to enhance this and future research endeavors. This collaboration, the Alabama Advanced Solvents Cluster (AASC) is on ongoing collaborative effort between many of the investigators.

36 MATERIALS SCIENCE↗

On-the-fly closed-loop materials discovery via Bayesian active learning

Active learning—the field of machine learning (ML) dedicated to optimal experiment design—has played a part in science as far back as the 18th century when Laplace used it to guide his discovery of celestial mechanics. In this work, we focus a closed-loop, active learning-driven autonomous system on another major challenge, the discovery of advanced materials against the exceedingly complex synthesis-processes-structure-property landscape. We demonstrate an autonomous materials discovery methodology for functional inorganic compounds which allow scientists to fail smarter, learn faster, and spend less resources in their studies, while simultaneously improving trust in scientific results and machine learning tools. This robot science enables science-over-the-network, reducing the economic impact of scientists being physically separated from their labs. The real-time closed-loop, autonomous system for materials exploration and optimization (CAMEO) is implemented at the synchrotron beamline to accelerate the interconnected tasks of phase mapping and property optimization, with each cycle taking seconds to minutes. We also demonstrate an embodiment of human-machine interaction, where human-in-the-loop is called to play a contributing role within each cycle. This work has resulted in the discovery of a novel epitaxial nanocomposite phase-change memory material.

36 MATERIALS SCIENCE↗

Integrated Framework to Enable Design Space Exploration of In-Space Transportation Architectures

Even with the recent shift in focus of NASA’s human spaceflight program towards the Moon, the long-term goal continues to be crewed missions to Mars. Regardless of the accepted architecture, in-space transportation systems are a critical portion to achieving this goal. An emphasis is placed on presenting decision makers with many options early on to make an informed down-selection. Although current processes are able to address any aspects of the challenging underlying multi-disciplinary analysis and optimization problem of these advanced concepts, they are unable to comprehensively perform design space exploration inexpensively,potentially leaving attractive alternatives on the table. A design framework is proposed that is capable of enabling the integrated mission analysis, vehicle sizing and synthesis problem for in-space transportation architectures. This framework is enabled through the use of the vehicle synthesis tool, Dynamic Rocket Equation Tool, various subsystem sizing models, and low-thrust trajectory optimization codes. As a case study to demonstrate the framework, two design points of a hybrid propulsion stage concept, studied by Georgia Tech’s 2018 Revolutionary Aerospace Systems Concepts-Academic Linkage team, is explored.

Akshay Prasad↗