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At least 199 records · Page 11

High Temperature, High Pressure Stability of Aqueous Foams for Potential Application in Enhanced Geothermal System (EGS)

Enhanced Geothermal Systems (EGS) are typically constructed by injecting high-pressure water into deep hot dry rocks (HDR) under carefully controlled conditions to create new or re-open existing fractures, which usually uses an immense quantity of water. In lieu, a more sustainable technique is to utilize aqueous foams as fracturing fluid to reduce water consumption and waste-water treatments of conventional hydraulic fracturing. Although foam-based fracturing has shown promising results in oil and gas industries, its feasibility is not demonstrated in EGS conditions that usually involve high temperature and high pressures. One potential barrier of utilizing foams in EGS applications is that foams are thermodynamically unstable and will become more unstable with increasing temperature due to liquid drainage, bubble coarsening, and coalescence. This work focuses on evaluation of the stability of selected aqueous foams under high-temperature and high-pressure conditions. Specifically, foams generated with surfactant alfa olefin sulfonate (AOS) were studied at temperature up to 200oC, while the pressure ranged between 100 psi and 1000 psi. The effect of additional stabilizing agents was also examined, including guar gum, bentonite clay, borate salt crosslinker, silicon dioxide nanoparticles (SiO2), and graphene oxide (GO) dispersion. Results showed that the stabilizing agents can enhance the foam thermal stability. Foams made with AOS and the borate salt crosslinker exhibited the longest half-life of 20 min at 200°C when the pressure was at 1000 psi. Data fitting showed that foam stability decreased exponentially as temperature increased. On the other hand, pressure increased the foam half-life which followed a power model. This study indicates that it may be possible to obtain highly stable foams at high-temperature and high-pressure conditions with appropriate stabilizing agents.

Thakore, Viren↗

Various Low-Symmetry Phases in High- χ and Conformationally Asymmetric PDMS- b -PTFEA Copolymers

Since the discovery of the Frank–Kasper (FK) phase a decade ago, single-component block copolymer systems have offered unique opportunities to explore the structural and phase-transition properties of topologically close-packed FK phases composed of point-particle motifs. Here, we present the formation of complex low-symmetry phases and their thermodynamic stability using high-χ and high-ε linear diblock copolymers, where χ and ε are the Flory–Huggins interaction parameter and conformational asymmetry between the two blocks, respectively. In this work, a series of polydimethylsiloxane-b-poly(2,2,2-trifluoroethyl acrylate) (PDMS-b-PTFEA) copolymers are prepared by tuning the volume fraction ($f_{\text{PTFEA}}$) of a minor PTFEA block. The packing structures of PDMS-b-PTFEAs are mapped in the space of temperature versus $f_{\text{PTFEA}}$ using X-ray scattering measurements. In addition to the packing structures reported earlier, we identify another A15 phase at higher $f_{\text{PTFEA}}$ close to a hexagonally packed cylinder (HEX) phase and establish the phase sequence of HEX–A15–σ–C14–BCC with decreasing $f_{\text{PTFEA}}$. Theoretical calculation of relative free-energy densities confirms the experimental phase sequence of the composition-dependent sphere-packing structures. Interestingly, the domain sizes of three-dimensional (3D) sphere-packing structures are nearly temperature-invariant compared to that of a two-dimensional HEX structure, and we attribute this dimensional stability to the strong enthalpic effects in the formation of 3D packing structures and the geometrical characteristics of spherical domains. Our results demonstrate that the interaction parameter χ, together with the known role of conformational asymmetry ε, serves as the primary thermodynamic parameter for selecting and stabilizing various low-symmetry packing structures in sphere-forming linear diblock copolymer systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Customizable Aperture Geometry in Metal–Organic Frameworks for Kinetic Hydrocarbon Separation

Precise control of aperture dimensions is crucial in adsorptive separations of hydrocarbons, as it directly affects key parameters such as selectivity, capacity, diffusion, and recyclability. The development of metal–organic frameworks (MOFs) has enabled the fine-tuning of local pore environments to address important hydrocarbon separations. However, customizing the aperture geometry to tune the kinetic separation performance remains challenging. Here, we deploy a mixed-linker synthesis strategy, combining long and short linkers on fcu net Zr-MOFs with equilateral triangular apertures to construct isoreticular multivariate MOFs, NU-415 and NU-416, with tailored isosceles triangular apertures suitable for the separation of hexane isomers. Sorption, liquid batch separation, and X-ray diffraction measurements demonstrate significantly improved selectivity, capacity, stability, and recyclability of NU-415 and NU-416 compared with Zr-muconate and MOF-801. Notably, both NU-415 and NU-416 achieve uptake capacities of 2.2 mmol g –1 in 1 min with an n-hexane to 2,2-dimethylbutane selectivity over 200 in an equimolar ternary mixture at ambient conditions, comparable to leading reported materials. Mechanistic studies confirm that separation performance is predominantly governed by significant kinetic differences rather than by thermodynamics. Furthermore, the successful customization of aperture geometry not only enables superior linear to monobranched hexane selectivity in NU-415 but also demonstrates the mixed-linker synthesis strategy as a promising solution for precise and predictable pore architecture control in MOFs.

Adsorption↗

Ethane dehydrogenation over manganese oxides supported on ZSM-5 zeolites

Mn-ZSM5 catalysts are shown to have high reaction rates, C 2 H 4 selectivity and stability for the ethane dehydrogenation reaction. The specific reaction rate increases with the Mn loading until the optimal Mn amount of 3.4 wt% for zeolites with a Si/Al ratio of 12. Structure characterizations and spectra analysis have unveiled that this catalyst contains MnO 2 nanoparticles on the zeolite external surface and (MnOH) + groups on the external surface of the zeolite. The MnO 2 nanoparticles contain the catalytic sites for ethane dehydrogenation while the (MnOH) + groups help stabilize the oxide particles, leading to the high stability of the Mn-ZSM5 catalyst for EDH. As a result, the Mn-ZSM5 samples can catalyze EDH for over 150 h at 600 °C with a high reaction rate (>10 mmol C 2 H 6 g cat –1 h –1 ) and high C 2 H 4 selectivity (>98%). Finally, the spent catalyst can also be regenerated by calcination in dry or wet air (3% steam).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe 0 ) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile-siderophile characteristics, where chalcophile-siderophile S served as a bridge to allow impregnating nFe 0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile-siderophile elements into the nFe 0 crystals are evidenced at both intraparticle and individual-particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity-selectivity-longevity-stability trade-off. Compared to nFe 0 , superhydrophobic Cu─S─nFe 0 with lattice expansion promoted dechlorination by 20-fold but inhibited HER by 150-fold, utilizing ≈80–100% electrons from the Fe 0 reservoir. This work demonstrates the concept of engineering nFe 0 lattice with tunable structure-property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoinduced Electron and Energy Transfer Pathways and Photocatalytic Mechanisms in Hybrid Plasmonic Photocatalysis

Hybrid plasmonic nanostructures are built on plasmonic metalnanostructures surrounded by catalytic metals or metal oxides. We report that recent studies have shown that hybrid plasmonic nanocatalysts can concurrently utilize thermal energy and photon stimuli and exhibit high catalytic activity, selectivity, and stability that are not attainable in conventional purely thermally activated catalytic processes. The hybrid plasmonic photocatalytic approach has recently emerged as an attractive concept for the conversion of solar energy into chemical energy, the distributed synthesis of valuable chemicals such as ammonia with little to no requirement of external heating, and the development of coke-resistant and selective catalytic processes. The field of hybrid plasmonic photocatalysis has grown tremendously in the last decade. In this review article, the advantages of visible-light-augmented hybrid plasmonic photocatalysis over conventional pure thermally activated heterogeneous catalysis are discussed. Fundamental insights are provided into photocatalytic mechanisms by which the photoexcited charge carriers (electrons and holes) are formed and transferred to adsorbates triggering chemical transformations on the surface of hybrid plasmonic nanocatalysts. Computational modeling used for predicting and understanding the photocatalytic activity and selectivity on hybrid plasmonic nanostructures is also reviewed. The review closes with a discussion of the current challenges, new opportunities, and future outlook for hybrid plasmonic photocatalysis.

36 MATERIALS SCIENCE↗

In Situ Engineering of Intracellular Hemoglobin for Implantable High-Performance Biofuel Cells

The key challenge for the broad application of implantable biofuel cells (BFCs) is to achieve inorganic–organic composite biocompatibility while improving the activity and selectivity of the catalysts. We have fabricated nanoengineered red blood cells (NERBCs) by an environmentally friendly method by using red blood cells as the raw material and hemoglobin (Hb) embedded with ultrasmall hydroxyapatite (HAP, Ca 10 (PO 4 ) 6 (OH) 2 ) as the functional BFC cathode material. The NERBCs showed greatly enhanced cell performance with high electrocatalytic activity, stability, and selectivity. The NERBCs maintained the original biological properties of the natural cell, while enhancing the catalytic oxygen reduction reaction (ORR) through the interaction between -OH groups in HAP and the Hb in RBCs. Finally, they also enabled direct electron transportation, eliminating the need for an electron-transfer mediator, and showed catalytic inactivity for glucose oxidation, thus potentially enabling the development of separator-free BFCs.

09 BIOMASS FUELS↗

Design and Analysis of Morpheus Lander Flight Control System

The Morpheus Lander is a vertical takeoff and landing test bed vehicle developed to demonstrate the system performance of the Guidance, Navigation and Control (GN&C) system capability for the integrated autonomous landing and hazard avoidance system hardware and software. The Morpheus flight control system design must be robust to various mission profiles. This paper presents a design methodology for employing numerical optimization to develop the Morpheus flight control system. The design objectives include attitude tracking accuracy and robust stability with respect to rigid body dynamics and propellant slosh. Under the assumption that the Morpheus time-varying dynamics and control system can be frozen over a short period of time, the flight controllers are designed to stabilize all selected frozen-time control systems in the presence of parametric uncertainty. Both control gains in the inner attitude control loop and guidance gains in the outer position control loop are designed to maximize the vehicle performance while ensuring robustness. The flight control system designs provided herein have been demonstrated to provide stable control systems in both Draper Ares Stability Analysis Tool (ASAT) and the NASA/JSC Trick-based Morpheus time domain simulation.

Jang, Jiann-Woei↗

Porous Carbon-Hosted Atomically Dispersed Iron-Nitrogen Moiety as Enhanced Electrocatalysts for Oxygen Reduction Reaction in a Wide Range of pH

As one of the alternatives to replace precious metal catalysts, transition-metal–nitrogen–carbon (M–N–C) electrocatalysts have attracted great research interest due to their low cost and good catalytic activities. Despite nanostructured M–N–C catalysts can achieve good electrochemical perfor-mances, they are vulnerable to aggregation and insufficient catalytic sites upon continuous catalytic reaction. In this work, metal–organic frameworks derived porous single-atom electrocatalysts (SAEs) were successfully prepared by simple pyrolysis procedure without any further posttreatment. Combining the X-ray absorption near-edge spectroscopy and electrochemical measure-ments, the SAEs have been identified with superior oxygen reduction reaction (ORR) activity and stability compared with Pt/C catalysts in alkaline condition. More impressively, the SAEs also show excellent ORR electrocatalytic perfor-mance in both acid and neutral media. This study of nonprecious catalysts provides new insights on nanoengineering catalytically active sites and porous structures for nonprecious metal ORR catalysis in a wide range of pH.

Environmental Molecular Sciences Laboratory↗

Stable and selective catalysts for propane dehydrogenation operating at thermodynamic limit

Hitting the limits on propene synthesis The greater abundance of propane from shale gas has spurred efforts to use it as a propylene feedstock. Direct dehydrogenation catalysts consisting of platinum–tin alloy nanoparticles supported on alumina often must run with hydrogen dilution to avoid carbon buildup and excess tin to avoid alloy segregation. Motagamwala et al. report that platinum–tin nanoparticles interact more weakly with a silica support and the metals thus do not segregate. The use of undiluted reactants allowed the reaction to run near the thermodynamically limit of about 67% conversion with a selectivity to propylene of more than 99%. This catalyst also does not build up carbon and could run up to 30 hours without deactivation. Science , abg7894, this issue p. 217

Science & Technology - Other Topics↗

Synthesis of ruthenium metal doped titanium dioxide nanoparticles for CO{sub 2} hydrogenation

Two different types of Ru metal doped TiO{sub 2} nanoparticles were synthesized using a sole gel method with and without ionic liquid. It was clearly observed during characterizing the Ru-TiO{sub 2}-IL catalyst with respect to Ru-TiO{sub 2} catalyst that Ru metal is dispersed while using ionic liquid as reaction medium for catalyst synthesis. TEM image also reveals the presence of agglomeration free, stable and well dispersed Ru metal doped TiO{sub 2} nanoparticles in Ru-TiO{sub 2}-IL over a Ru-TiO{sub 2} catalyst. Such unique feature of the Ru-TiO{sub 2}-IL catalyst reflected in terms of high TON /TOF value of formic acid during the hydrogenation reaction of CO{sub 2} in task specific ionic liquid medium. Low catalysts loading, moisture/air stability, high selectivity, an easy reaction protocol for catalyst synthesis as well as stress-free reaction condition along with 6 times catalysts recycling is the major outcomes of the proposed protocol.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Ares I Flight Control System Design

The Ares I launch vehicle represents a challenging flex-body structural environment for flight control system design. This paper presents a design methodology for employing numerical optimization to develop the Ares I flight control system. The design objectives include attitude tracking accuracy and robust stability with respect to rigid body dynamics, propellant slosh, and flex. Under the assumption that the Ares I time-varying dynamics and control system can be frozen over a short period of time, the flight controllers are designed to stabilize all selected frozen-time launch control systems in the presence of parametric uncertainty. Flex filters in the flight control system are designed to minimize the flex components in the error signals before they are sent to the attitude controller. To ensure adequate response to guidance command, step response specifications are introduced as constraints in the optimization problem. Imposing these constraints minimizes performance degradation caused by the addition of the flex filters. The first stage bending filter design achieves stability by adding lag to the first structural frequency to phase stabilize the first flex mode while gain stabilizing the higher modes. The upper stage bending filter design gain stabilizes all the flex bending modes. The flight control system designs provided here have been demonstrated to provide stable first and second stage control systems in both Draper Ares Stability Analysis Tool (ASAT) and the MSFC 6DOF nonlinear time domain simulation.

Jang, Jiann-Woei↗

High-Temperature Properties and Microstructural Stability of the AISI H13 Hot-Work Tool Steel Processed by Selective Laser Melting

The microstructural stabilities, softening resistance, and high-temperature tensile properties of the H13 hot-work tool steel by selective laser melting (SLM) were systematically studied. A series of tempering procedures were performed on the as-SLMed specimens. Afterwards, the mechanism of softening resistance behavior was discussed based on the XRD, SEM, EBSD observations, hardness measurements, and high-temperature tensile tests. It was found that the as-SLMed H13 consisted of α-iron and γ-iron. The carbide-stabilizing elements aggregated as the cell-like substructures for the rapid solidification of the SLM process. After the softening resistance treatment, the retained austenite transformed to ferrite and carbide mixtures. The cell-like substructures dissolved slowly into the matrix when the temperature was below 550 °C. These factors increased the hardness and retarded the softening of the material. When the temperature was 600 °C, the microstructural constituents transformed to soft ferrite and globular carbides, which lead to a considerable decrease of the hardness. Due to the grain refinement, solid solution strengthening, and residual stress, the as-SLMed H13 exhibited better mechanical properties than that of the wrought counterparts.

36 MATERIALS SCIENCE↗

Nickel@Siloxene catalytic nanosheets for high-performance CO 2 methanation

Two-dimensional (2D) materials are of considerable interest for catalyzing the heterogeneous conversion of CO 2 to synthetic fuels. In this regard, 2D siloxene nanosheets, have escaped thorough exploration, despite being composed of earth-abundant elements. Herein we demonstrate the remarkable catalytic activity, selectivity, and stability of a nickel@siloxene nanocomposite; it is found that this promising catalytic performance is highly sensitive to the location of the nickel component, being on either the interior or the exterior of adjacent siloxene nanosheets. Control over the location of nickel is achieved by employing the terminal groups of siloxene and varying the solvent used during its nucleation and growth, which ultimately determines the distinct reaction intermediates and pathways for the catalytic CO 2 methanation. Significantly, a CO 2 methanation rate of 100 mmol gNi –1 h –1 is achieved with over 90% selectivity when nickel resides specifically between the sheets of siloxene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Communication: A density functional investigation of structure-property evolution in the tetrakis hexahedral C{sub 4}Al{sub 14} nanocluster

Nanoclusters are prime objects of study in modern nanotechnology and offer a variety of applications promoted by their properties tunable by size, shape, and composition. DFT calculations are employed to analyze structure, stability, and selected electronic properties of a core-shell C{sub 4}Al{sub 14} species. With insertion of the carbon core, the original low-symmetry aluminum cluster is predicted to undergo a considerable reshaping and acquire a striking D{sub 4h} tetrakis-hexahedral geometry, with proportions controlled by a near-degenerate spin state or charge. The system also becomes more stable to dissociation. Surprisingly, other properties such as ionisation energy and electron affinity do not change significantly, although still exhibit some interesting features including opposite variations for vertical and adiabatic values. The stability and property evolutions are analyzed in terms of contributions from reshaping of the shell and its further interaction with the core. The system thus has potential applications as a symmetric building unit and a molecular device for nano-electronics/spintronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation stability test on multiphase glass ceramic and crystalline ceramic waste forms

A radiation stability study was performed on glass ceramic and crystalline ceramic waste forms. These materials are candidate host materials for immobilizing alkali/alkaline earth (Cs/Sr-CS) + lanthanide (LN) + transition metal (TM) fission product waste streams from nuclear fuel reprocessing. In this study, glass ceramics were fabricated using a borosilicate glass as a matrix in which to incorporate CS/LN/TM combined waste streams. The major phases in these multiphase materials are powellite, oxyaptite, pollucite, celsian, and durable residual glass phases. Al2O3 and TiO2 were combined with these waste components to produce multiphase crystalline ceramics containing hollandite-type phases, perovskites, pyrochlores and other minor metal titanate phases. For the radiation stability test, selected glass ceramic and crystalline ceramic samples were exposed to different irradiation environments including low fluxes of high-energy (~1–5 MeV) protons and alpha particles generated by an ion accelerator, high fluxes of low-energy (hundreds of keV) krypton particles generated by an ion implanter, and in-situ electron irradiations in a transmission electron microscope. These irradiation experiments were performed to simulate self-radiation effects in a waste form. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction and transmission electron microscopy. Our preliminary results reveal different radiation tolerance in different crystalline phases under various radiation damage environments. However, their stability may be rate dependent which may limit the waste loading that can be achieved.

Crystalline ceramic↗