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Results for “switchable selectivity”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Photocatalytic Methanol Dehydrogenation with Switchable Selectivity

Switchable selectivity achieved by altering reaction conditions within the same photocatalytic system offers great advantages for sustainable chemical transformations and renewable energy conversion. In this study, we investigate an efficient photocatalytic methanol dehydrogenation with controlled selectivity by varying the concentration of nickel cocatalyst, using zinc indium sulfide nanocrystals as a semiconductor photocatalyst, which enables the production of either formaldehyde or ethylene glycol with high selectivity. Control experiments revealed that formaldehyde is initially generated and can either serve as a terminal product or intermediate in producing ethylene glycol, depending on the nickel concentration in the solution. Mechanistic studies suggest a unique role of ionic nickel as an additional photoelectron competitor that can significantly influence selectivity, alongside its well-established function as a hydrogen evolution reaction cocatalyst under photocatalytic conditions. The demonstrated switchable selectivity provides a new tool for producing diverse products from methanol, while advancing the understanding of cocatalyst behavior for versatile catalytic performance.

Luo, Jie↗

Enhanced Laplace Pressures for Functional Surfaces: Wicking, Switchability, and Selectivity

Abstract Wetting functionalities of rough surfaces are largely determined by the Laplace pressure generated across liquid–gas interfaces formed within surface structures. Typically, rough wetting surfaces create negative Laplace pressures, enabling capillary wicking, while rough non‐wetting surfaces create positive Laplace pressures, exhibiting fluid repellency. Here, with microfabricated reentrant structures, it is shown that the same surface can exhibit either a negative or positive Laplace pressure, regardless of its intrinsic wettability. This material‐independent Laplace pressure duality enables or enhances a range of wetting functionalities including wicking, switchability, and selectivity. On the same surface, capillary rise, capillary dip, and the combination of the two which leads to further enhancement of the total sustainable capillary height and Laplace pressure, the driving force for wicking is demonstrated. Further, active switching of wetting states between the hemiwicking and the repellent Cassie state on reentrant structures is shown. Moreover, with a water‐hexane mixture system, selective wetting of reentrant structures are demonstrated, that is, water can be selectively wicked or repelled in the presence of hexane, and vice versa. These functionalities are achieved, which would typically require complex chemical coatings, solely using surface structures, thus largely expanding the design space for a wide range of thermofluidic applications.

36 MATERIALS SCIENCE↗

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗

Selective heterogeneous capture and release of actinides using carborane-functionalized electrodes

Here we report the heterogenization of molecular, electrochemically switchable ortho-substituted carboranes ( PO Cb, PO Cb-Pyr) for selective metal capture. Films of PO Cb and PO Cb-Pyr on glassy carbon and carbon fiber (CF) electrodes demonstrated heterogeneous electrochemical behaviour that was enhanced by the inclusion of single-walled carbon nanotubes (CNTs). Galvanostatically charged CF|CNT| PO Cb and CF|CNT| PO Cb-Pyr electrodes selectively captured and released actinides (Th 4+ , UO 2 2+ ) from mixed solutions containing alkali (Cs + ), lanthanide (Nd 3+ , Sm 3+ ) and actinide (Th 4+ , UO 2 2+ ) metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗

Switchable rocker arm

A rocker arm includes an outer arm and an inner arm which selectively pivots relative to the outer arm. The rocker arm also includes a lock pin which is displaced along a lock pin axis between a coupled position and a decoupled position. The rocker arm also includes a linkage and a linkage guide which guides the linkage along a linkage axis. One surface of the linkage engages an actuator while another surface of the linkage engages the lock pin such that the linkage translates motion from the actuator to motion of the lock pin.

42 ENGINEERING↗

Reversible non-volatile switch based on a TCNQ charge transfer complex

A solid-state synaptic memory matrix (10) having switchable weakly conductive connections at each node (24) whose resistances can be selectably increased or decreased over several orders of magnitude by control signals of opposite polarity, and which will remain stable after the signals are removed, comprises an insulated substrate (16), a set of electrical conductors (14) upon which is deposited a layer (18) of an organic conducting polymer, which changes from an insulator to a conductor upon the transfer of electrons, such as polymerized pyrrole doped with 7,7,8,8-tetracyanoquinodimethane (TCNQ), covered by a second set of conductors (20) laid at right angles to the first.

Nagasubramanian, Ganesan↗

Switchable resolution in soft x-ray tomography of single cells

The diversity of living cells, in both size and internal complexity, calls for imaging methods with adaptable spatial resolution. Soft x-ray tomography (SXT) is a three-dimensional imaging technique ideally suited to visualizing and quantifying the internal organization of single cells of varying sizes in a near-native state. The achievable resolution of the soft x-ray microscope is largely determined by the objective lens, but switching between objectives is extremely time-consuming and typically undertaken only during microscope maintenance procedures. Since the resolution of the optic is inversely proportional to the depth of focus, an optic capable of imaging the thickest cells is routinely selected. This unnecessarily limits the achievable resolution in smaller cells and eliminates the ability to obtain high-resolution images of regions of interest in larger cells. Here, we describe developments to overcome this shortfall and allow selection of microscope optics best suited to the specimen characteristics and data requirements. We demonstrate that switchable objective capability advances the flexibility of SXT to enable imaging cells ranging in size from bacteria to yeast and mammalian cells without physically modifying the microscope, and we demonstrate the use of this technology to image the same specimen with both optics.

59 BASIC BIOLOGICAL SCIENCES↗

Selective Electrochemical Capture and Release of Uranyl in Solution (Final Report)

The goal of this project is to investigate the selective, electrochemical capture and release of uranyl ((UO 2 ) 2 +) from biphasic or heterogeneous mixtures using a class of cluster molecules, ortho-carboranes (Cb), containing selective binding groups. Possible applications in PUREX, seawater uranyl extraction, or in actinide/lanthanide (An/Ln) or Ln/Ln separations are envisioned. With this funding, we sought to achieve these goals by harnessing the redox-switchable chelating properties of the “closo” Cb to the reduced “nido” Cb enabling the electrochemical control of the ligand bite angle. Using this premise, specific goals include: 1) integrating new selective coordinating groups (L) onto the carbon positions of Cb for the selective capture and release of uranyl, and; 2) anchoring these selective carboranes onto electrode and/or heterogeneous surfaces for the selective, heterogeneous capture and release of uranyl from aqueous solutions under flow conditions. Overall, this work focuses on advancing our understanding and controlling the properties of this new platform for metal capture and release chemistry which, we believe, has the potential for broader applicability in the separation sciences.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Lanthanide binding peptide surfactants at air–aqueous interfaces for interfacial separation of rare earth elements

Rare earth elements (REEs) are critical materials to modern technologies. They are obtained by selective separation from mining feedstocks consisting of mixtures of their trivalent cation. We are developing an all-aqueous, bioinspired, interfacial separation using peptides as amphiphilic molecular extractants. Lanthanide binding tags (LBTs) are amphiphilic peptide sequences based on the EF-hand metal binding loops of calcium-binding proteins which complex selectively REEs. We study LBTs optimized for coordination to Tb 3+ using luminescence spectroscopy, surface tensiometry, X-ray reflectivity, and X-ray fluorescence near total reflection, and find that these LBTs capture Tb 3+ in bulk and adsorb the complex to the interface. Molecular dynamics show that the binding pocket remains intact upon adsorption. We find that, if the net negative charge on the peptide results in a negatively charged complex, excess cations are recruited to the interface by nonselective Coulombic interactions that compromise selective REE capture. If, however, the net negative charge on the peptide is −3, resulting in a neutral complex, a 1:1 surface ratio of cation to peptide is achieved. Surface adsorption of the neutral peptide complexes from an equimolar mixture of Tb 3+ and La 3+ demonstrates a switchable platform dictated by bulk and interfacial effects. The adsorption layer becomes enriched in the favored Tb 3+ when the bulk peptide is saturated, but selective to La 3+ for undersaturation due to a higher surface activity of the La 3+ complex.

Ortuno Macias, Luis E. (ORCID:0000000284342192)↗

A new code for Galileo

Over the past six to eight years, an extensive research effort was conducted to investigate advanced coding techniques which promised to yield more coding gain than is available with current NASA standard codes. The delay in Galileo's launch due to the temporary suspension of the shuttle program provided the Galileo project with an opportunity to evaluate the possibility of including some version of the advanced codes as a mission enhancement option. A study was initiated last summer to determine if substantial coding gain was feasible for Galileo and, is so, to recommend a suitable experimental code for use as a switchable alternative to the current NASA-standard code. The Galileo experimental code study resulted in the selection of a code with constant length 15 and rate 1/4. The code parameters were chosen to optimize performance within cost and risk constraints consistent with retrofitting the new code into the existing Galileo system design and launch schedule. The particular code was recommended after a very limited search among good codes with the chosen parameters. It will theoretically yield about 1.5 dB enhancement under idealizing assumptions relative to the current NASA-standard code at Galileo's desired bit error rates. This ideal predicted gain includes enough cushion to meet the project's target of at least 1 dB enhancement under real, non-ideal conditions.

Dolinar, S.↗

Ionic Control over Ferroelectricity in 2D Layered van der Waals Capacitors

The van der Waals layered material CuInP 2 S 6 features interesting functional behavior, including the existence of four uniaxial polarization states, polarization reversal against the electric field through Cu ion migration, a negative-capacitance regime, and reversible extraction of Cu ions. At the heart of these characteristics lies the high mobility of Cu ions, which also determines the spontaneous polarization. Therefore, Cu migration across the lattice results in unusual ferroelectric behavior. Here, we demonstrate how the interplay of polar and ionic properties provides a path to ionically controlled ferroelectric behavior, achieved by applying selected DC voltage pulses and subsequently probing ferroelectric switching during fast triangular voltage sweeps. Using current measurements and theoretical calculations, we observe that increasing DC pulse duration results in higher ionic currents, the buildup of an internal electric field that shifts polarization loops, and an increase in total switchable polarization by ~50% due to the existence of a high polarization phase which is stabilized by the internal electric field. Apart from tuning ferroelectric behavior by selected square pulses, hysteretic polarization switching can even be entirely deactivated and reactivated, resulting in three-state systems where polarization switching is either inhibited or can be performed in two different directions.

36 MATERIALS SCIENCE↗

Enhanced spectral efficiency using bandwidth switchable SAW filtering for mobile satellite communications systems

Currently proposed mobile satellite communications systems require a high degree of flexibility in assignment of spectral capacity to different geographic locations. Conventionally this results in poor spectral efficiency which may be overcome by the use of bandwidth switchable filtering. Surface acoustic wave (SAW) technology makes it possible to provide banks of filters whose responses may be contiguously combined to form variable bandwidth filters with constant amplitude and phase responses across the entire band. The high selectivity possible with SAW filters, combined with the variable bandwidth capability, makes it possible to achieve spectral efficiencies over the allocated bandwidths of greater than 90 percent, while retaining full system flexibility. Bandwidth switchable SAW filtering (BSSF) achieves these gains with a negligible increase in hardware complexity.

Peach, Robert↗

Colloquium : Physical properties of group-IV monochalcogenide monolayers

The state-of-the-art knowledge of ferroelectric and ferroelastic group-IV monochalcogenide monolayers is surveyed. These semiconductors feature remarkable structural and mechanical properties, such as a switchable in-plane spontaneous polarization, soft elastic constants, structural degeneracies, and thermally driven two-dimensional structural transformations. Additionally, these 2D materials display selective valley excitations, valley Hall effects, and persistent spin helix behavior. After a description of their Raman spectra, a discussion of optical properties arising from their lack of centrosymmetry (such as an unusually strong second-harmonic intensity, large bulk photovoltaic effects, photostriction, and tunable exciton binding energies) is provided as well. Here, the physical properties observed in these materials originate from (correlate with) their intrinsic and switchable electric polarization, and the physical behavior hereby reviewed could be of use in nonvolatile memory, valleytronic, spintronic, and optoelectronic devices: these 2D multiferroics enrich and diversify the 2D material toolbox.

2D ferroelectrics↗

Switchable rocker arm

A rocker arm includes an outer arm defining a lock pin bore which is centered about a lock pin bore axis and an inner arm which selectively pivots relative to the outer arm about a pivot axis which is parallel to the lock pin bore axis. The inner arm includes a protrusion which defines an inner arm stop surface which is planar. A lock pin is disposed within the lock pin bore, the lock pin having a lock pin slot extending there into and also having a lock pin stop surface which is planar. The lock pin is displaced within the lock pin bore between a coupled position in which the lock pin stop surface is aligned with the inner arm stop surface and a decoupled position in which the lock pin slot is aligned with the protrusion.

42 ENGINEERING↗

Deciphering a Reaction Network for the Switchable Production of Tetrahydroquinoline or Quinoline with MOF-Supported Pd Tandem Catalysts

A mechanistic study of heterogeneous tandem catalytic systems is crucial for understanding and improving catalyst activity and selectivity but remains challenging. Here, we demonstrate that a thorough mechanistic study of a multistep reaction can guide us to the controllable selective synthesis of phenyltetrahydroquinoline or phenylquinoline with easily accessible precursors. The one-pot production can be achieved, catalyzed by a well-defined, bifunctional metal–organic framework-supported Pd nanoparticles, with only water as the side product. Our mechanistic study identifies six transient intermediates and ten transformation steps from the operando magic angle spinning nuclear magnetic resonance study under 27.6 bar H 2 . In particular, reactive intermediate 2-phenyl-3,4-dihydroquinoline cannot be observed with conventional chromatographic techniques but is found to reach the maximal concentration of 0.11 mol L –1 under the operando condition. The most probable reaction network is further deduced based on the kinetic information of reaction species, obtained from both operando and ex situ reaction studies. This deep understanding of the complex reaction network enables the kinetic control of the conversions of key intermediate, 2-phenyl-3,4-dihydroquinoline, with the addition of a homogeneous co-catalyst, allowing the selective production of tetrahydroquinoline or quinoline on demand. Finally, the demonstrated methods in this work open up new avenues toward efficient modulation of reactions with a complex network to achieve desired selectivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗