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At least 1,441 records · Page 80

Tunable metal hydroxide–organic frameworks for catalysing oxygen evolution

The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide–organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π–π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80A $g^{-1}_{catalyst}$ 1 at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.

36 MATERIALS SCIENCE↗

Effect of a Cr-rich surface layer on D retention in various RAFM steels

In this work, deuterium (D) retention is compared between various reduced-activation ferritic/martensitic steels, including CLF-1, Eurofer, F82H, and Rusfer, exposed to pure D plasma (ion flux ~1.5–2 × 10 21 m -2 s -1 , fluence, ϕ D , ~1 × 10 25 m -2 , sample temperature ~373 K, and incident ion energy ~100 eV). It is found that there is a large difference (up to ~30x) in the D retention between CLF-1 and F82H even with the same plasma exposure condition and similar nominal composition. The ϕ D dependence of the D retention exhibits a peculiar, counterintuitive feature: the D retention decreases with an increase in ϕ D from 2 × 10 23 m -2 to 1 × 10 25 m -2 . Surface analyses reveal that a Cr-rich surface layer is formed during outgassing at 773 K for 1 h before plasma exposure, and that there exists a clear correlation between the D retention and the Cr content in the surface layer.

36 MATERIALS SCIENCE↗

Harnessing Quantum Capacitance in 2D Material/Molecular Layer Junctions for Novel Electronic Device Functionality

Two-dimensional (2D) materials promise advances in electronic devices beyond Moore’s scaling law through extended functionality, such as non-monotonic dependence of device parameters on input parameters. However, the robustness and performance of effects like negative differential resistance (NDR) and anti-ambipolar behavior have been limited in scale and robustness by relying on atomic defects and complex heterojunctions. In this paper, we introduce a novel device concept that utilizes the quantum capacitance of junctions between 2D materials and molecular layers. We realized a variable capacitance 2D molecular junction (vc2Dmj) diode through the scalable integration of graphene and single layers of stearic acid. The vc2Dmj exhibits NDR with a substantial peak-to-valley ratio even at room temperature and an active negative resistance region. The origin of this unique behavior was identified through thermoelectric measurements and ab initio calculations to be a hybridization effect between graphene and the molecular layer. The enhancement of device parameters through morphology optimization highlights the potential of our approach toward new functionalities that advance the landscape of future electronics.

2D materials↗

Quasi-Liquid Layer Formation on Ice under Stratospheric Conditions

Characterization of the interaction of hydrogen chloride (HCl) with ice is essential to understanding at a molecular level the processes responsible for ozone depletion involving polar stratospheric cloud (PSC) particles. To explain the catalytic role PSC particle surfaces play during chlorine activation, we proposed previously that HCl induces the formation of a disordered region on the ice surface, a quasi-liquid layer (QLL), at stratospheric conditions. The QLL is known to exist in pure ice crystals at temperatures near the melting point, but its existence at stratospheric temperatures (-85 C to -70 C) had not been reported yet. We studied the interaction of HCl with ice under stratospheric conditions using the complementary approach of a) ellipsometry to directly monitor the ice surface, using chemical ionization mass spectrometry (CIMS) to monitor the gas phase species present in the ellipsometry experiments, and b) flow-tube experiments with CIMS detection. Here we show that trace amounts of HCl induce QLL formation at stratospheric temperatures, and that the QLL enhances the chlorine-activation reaction of HCl with chlorine nitrate (ClONO2), and also enhances acetic acid (CH3COOH) adsorption.

McNeill, V. Faye↗

Soil resistance and recovery during neotropical forest succession

The recovery of soil conditions is crucial for successful ecosystem restoration and, hence, for achieving the goals of the UN Decade on Ecosystem Restoration. Here, we assess how soils resist forest conversion and agricultural land use, and how soils recover during subsequent tropical forest succession on abandoned agricultural fields. Our overarching question is how soil resistance and recovery depend on local conditions such as climate, soil type and land-use history. For 300 plots in 21 sites across the Neotropics, we used a chronosequence approach in which we sampled soils from two depths in old-growth forests, agricultural fields (i.e. crop fields and pastures), and secondary forests that differ in age (1–95 years) since abandonment. We measured six soil properties using a standardized sampling design and laboratory analyses. Soil resistance strongly depended on local conditions. Croplands and sites on high-activity clay (i.e. high fertility) show strong increases in bulk density and decreases in pH, carbon (C) and nitrogen (N) during deforestation and subsequent agricultural use. Resistance is lower in such sites probably because of a sharp decline in fine root biomass in croplands in the upper soil layers, and a decline in litter input from formerly productive old-growth forest (on high-activity clays). Soil recovery also strongly depended on local conditions. During forest succession, high-activity clays and croplands decreased most strongly in bulk density and increased in C and N, possibly because of strongly compacted soils with low C and N after cropland abandonment, and because of rapid vegetation recovery in high-activity clays leading to greater fine root growth and litter input. Furthermore, sites at low precipitation decreased in pH, whereas sites at high precipitation increased in N and decreased in C : N ratio. Extractable phosphorus (P) did not recover during succession, suggesting increased P limitation as forests age. These results indicate that no single solution exists for effective soil restoration and that local site conditions should determine the restoration strategies.

60 APPLIED LIFE SCIENCES↗

Current state and future trends in boundary layer control on lifting surfaces

Successful flow control may bring numerous benefits, such as flow stabilization, flow reattachment, separation delay, drag reduction, lift increase, aerodynamic performance improvement, energy efficiency increase, shock delay or weakening, noise reduction, etc. For these purposes, many different flow control devices, which can be classified as passive, semi-active and active, have been designed and tested. This review paper aims to highlight the most promising and commonly employed boundary layer control methods as well as outline their potential in specific applications in aerospace and energy engineering. Referenced studies, performed on various geometries (flat plates, channels, airfoils, wings, blades, cylinders), are primarily numerical or experimental. Although enhanced aerodynamic performance is achieved in many cases, further research is required to draw general conclusions. This paper aims to demonstrate that, in the future, we may expect further developments of flow control actuators, as well as their increased application.

42 ENGINEERING↗

Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes

A method of making a passively impact resistant composite electrolyte and separator layer includes providing a suspension composition including electrically non-conducting particles that enable shear thickening. The particles can have a polydispersity index of no greater than 0.1, an average particle size in a range of from 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. A particle suspension solvent is provided for suspending the particles. The suspension composition is applied to a porous separator material. A portion of the particles and suspension solvent penetrate the pores and the remainder of the particles in the suspension composition are distributed across the surface of the separator material. The suspension solvent is evaporated from the separator material to provide a shear thickening particle loaded separator. A separator assembly and a passivated battery are also disclosed.

25 ENERGY STORAGE↗

Fabrication of films and coatings used to activate shear thickening, impact resistant electrolytes

A method of making a passively impact resistant composite electrolyte and separator layer includes providing a suspension composition including electrically non-conducting particles that enable shear thickening. The particles can have a polydispersity index of no greater than 0.1, an average particle size in a range of from 50 nm to 1 um, and an absolute zeta potential of greater than ±40 mV. A particle suspension solvent is provided for suspending the particles. The suspension composition is applied to a porous separator material. A portion of the particles and suspension solvent penetrate the pores and the remainder of the particles in the suspension composition are distributed across the surface of the separator material. The suspension solvent is evaporated from the separator material to provide a shear thickening particle loaded separator. A separator assembly and a passivated battery are also disclosed.

Armstrong, Beth L.↗

Resolving Chemical and Spatial Heterogeneities at Complex Electrochemical Interfaces in Li-Ion Batteries

The high specific capacities of Ni-rich transition metal oxides have garnered immense interest for improving the energy density of Li-ion batteries (LIBs). Despite the potential of these materials, Ni-rich cathodes suffer from interfacial instabilities that lead to crystallographic rearrangement of the active material surface as well as the formation of a cathode electrolyte interphase (CEI) layer on the composite during electrochemical cycling. While changes in crystallographic structure can be detected with diffraction-based methods, probing the chemistry of the disordered, heterogeneous CEI layer is challenging. In this work, we use a combination of ex situ solid-state nuclear magnetic resonance (SSNMR) spectroscopy and X-ray photoemission electron microscopy (XPEEM) to provide chemical and spatial information, on the nanometer length scale, on the CEI deposited on LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) composite cathode films. XPEEM elemental maps offer insight into the lateral arrangement of the electrolyte decomposition products that comprise the CEI and paramagnetic interactions (assessed with electron paramagnetic resonance (EPR) and relaxation measurements) in 13 C SSNMR provide information on the radial arrangement of the CEI from the NMC811 particles outward. Using this approach, here we find that LiF, Li 2 CO 3 , and carboxy-containing structures are directly appended to NMC811 active particles, whereas soluble species detected during in situ 1 H and 19 F solution NMR experiments (e.g., alkyl carbonates, HF, and vinyl compounds) are randomly deposited on the composite surface. We show that the combined approach of ex situ SSNMR and XPEEM, in conjunction with in situ solution NMR, allows spatially-resolved, molecular-level characterization of paramagnetic surfaces and new insights into electrolyte oxidation mechanisms in porous electrode films.

36 MATERIALS SCIENCE↗

Few-layer tin sulfide (SnS): Controlled synthesis, thickness dependent vibrational properties, and ferroelectricity

Group IV monochalcogenides, anisotropic van der Waals crystals (and black phosphorus analogues), are attracting increasing interest due to a number of exceptional properties including anisotropic optoelectronics and multiferroicity predicted and in part realized in the ultrathin limit. Due to their enhanced chemical reactivity, both exfoliation and synthesis of monolayer and few-layer crystals pose challenges not found in other 2D/layered materials, such as the transition metal dichalcogenides. In this work, we show that SnS synthesis on SnS 2 van der Waals substrates can address these challenges and consistently produces few-layer flakes, a capability that is explained via analysis of real-time microscopy of the growth process. Raman spectroscopy combined with efficient computations of the Raman-active modes across an extended thickness range enables a comprehensive understanding of the evolution of the vibrational properties of SnS with number of layers. Lateral piezoresponse force microscopy provides unprecedented insight into the stacking-dependent polarization and ferroelectric domain structures in large few-layer SnS flakes. The combined results establish a basis for further fundamental studies and applications of SnS and other group IV monochalcogenides in the few-layer regime.

36 MATERIALS SCIENCE↗

Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss

Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). Here, in this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO 3 2- /SO 4 2- redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.

25 ENERGY STORAGE↗

Templated Growth and Passivation of Vertically Oriented Antimony Selenide Thin Films for High-Efficiency Solar Cells in Substrate Configuration

Antimony selenide (Sb 2 Se 3 ) is a promising low-cost photovoltaic material with a 1D crystal structure. The grain orientation and defect passivation play a critical role in determining the performance of polycrystalline Sb 2 Se 3 thin-film solar cells. In this work, a seed layer is introduced on a molybdenum (Mo) substrate to template the growth of a vertically oriented, columnar Sb 2 Se 3 absorber layer by closed space sublimation. By controlling the grain orientation and compactness of the Sb 2 Se 3 seeds, obtain high-quality Sb 2 Se 3 absorber layers with passive Sb 2 Se 3 /Mo interfaces is obtained, which in turn improve the transport of photoexcited charge carriers through the absorber layer and its interfaces. Post-deposition annealing of absorber layers in ambient air is further utilized to passivate the defects in Sb 2 Se 3 and enhance the quality of the front heterojunction. As a result of systematic processing optimization, Sb 2 Se 3 planar heterojunction solar cells are fabricated in substrate configuration with a champion power conversion efficiency of 8.5%.

14 SOLAR ENERGY↗

Active Fail-Safe Micro-Array Flow Control for Advanced Embedded Propulsion Systems

The primary objective of this research effort was to develop and analytically demonstrate enhanced first generation active "fail-safe" hybrid flow-control techniques to simultaneously manage the boundary layer on the vehicle fore-body and to control the secondary flow generated within modern serpentine or embedded inlet S-duct configurations. The enhanced first-generation technique focused on both micro-vanes and micro-ramps highly-integrated with micro -jets to provide nonlinear augmentation for the "strength' or effectiveness of highly-integrated flow control systems. The study focused on the micro -jet mass flow ratio (Wjet/Waip) range from 0.10 to 0.30 percent and jet total pressure ratios (Pjet/Po) from 1.0 to 3.0. The engine bleed airflow range under study represents about a 10 fold decrease in micro -jet airflow than previously required. Therefore, by pre-conditioning, or injecting a very small amount of high-pressure jet flow into the vortex generated by the micro-vane and/or micro-ramp, active flow control is achieved and substantial augmentation of the controlling flow is realized.

Anderson, Bernhard H.↗

Fabrication of high-performance gas-diffusion-electrode based membrane-electrode assemblies

This paper demonstrates the fabrication and processing steps required to produce high performance fuel cell membrane electrode assemblies (MEAs) based on spray-coated gas-diffusion electrodes (GDEs). It is demonstrated that coating the catalyst layer with a thin layer of ionomer and then hot pressing the GDEs to the membrane is required to achieve comparable catalyst activity and air performance to catalyst-coated-membrane MEAs. We show that there is a critical amount of ionomer required to achieve maximized performance. Using electron microscopy, we show that the combination of the ionomer overlayer and hot-pressing bonds the catalyst layer to the membrane, increasing the interfacial contact area and quality of this interface. We also find that the ionomer overlayer smooths the surface of the GDE and provides increased contact area between the GDE and the membrane. Additionally, we demonstrate that much less ionomer is required for high-performance than has been previously reported. Through model fitting of electrochemical impedance spectroscopy, we show that this improvement in the catalyst layer - membrane interface reduces the effective catalyst layer resistance, which reduces Ohmic losses and increases catalyst utilization.

33 ADVANCED PROPULSION SYSTEMS↗

SILICON CARBIDE THERMOMETRY USING RAMAN SPECTROSCOPY ON IRRADIATED TRISO PARTICLES

Silicon carbide (SiC) passive thermometry has emerged as a promising post-irradiation examination (PIE) technique for estimating irradiation temperature near the end of irradiation. While dilatometry techniques have been traditionally used to analyze prismatic samples after irradiation, Raman spectroscopy has recently been shown to provide comparable results by analyzing Raman-active phonon modes. In this work, Raman spectroscopy has been applied to the SiC layer of cross-sectioned irradiation tristructural isotropic (TRISO) particles from the AGR-5/6/7 experiment to evaluate the feasibility of particle-scale passive thermometry. Two-dimensional Raman mapping was used to measure the position of the SiC longitudinal optical (LO) phonon, which was then converted to an apparent irradiation temperature using a previously established empirical correlation. Particles from AGR-5/6/7 Compacts 2-2-1 and 5-1-3 were selected as their calculated time-averaged, volume-averaged (TAVA) temperatures (828°C and 706°C, respectively) fall within the range of the sensitivity of the experimental approach. The use of SiC thermometry was anticipated to confirm or highlight potential deviations from calculated end-of-life TAVA temperature across compacts. Four particles from Compact 2-2-1 and two particles from Compact 5-1-3 were selected based on 110mAg inventory (either some measurable activity or below the minimum detection limit) which is commonly used as an indicator of in-pile temperature variation of particles within the same compact. Across every particle selected it was determined that the average LO peak position was located around 968 cm-1 to 969 cm-1. Using the previously determined empirical correlation, this corresponds to an irradiation temperature around 950°C to 966°C, which does not align with the reported TAVA temperature values. This discrepancy in apparent irradiation temperatures likely reflects a combination of uncertainties in the calculated particle temperatures and differences in irradiation history between the present specimens and those used to establish the empirical Raman calibration such as neutron flux (damage rate) and SiC microstructure (as fabricated and irradiated).

Vawdrey, Josh [ORNL]↗

Numerical investigation of sound transmission through double wall cylinders with respect to active noise control

Market pressure for more fuel efficient air travel has led to increased use of turboprop and higher bypass turbofan engines. The low frequency components of propeller, jet and boundary layer noise are difficult to attenuate with conventional passive techniques. Weight and geometric restrictions for sound absorbing meterials limit the amount and type of treatment that may be applied. An active noise control (ANC) method is providing to be an attractive alternative. The approach taken in this paper uses a numerical finite/boundary element method (FEM/BEM) that may be easilty adapted to arbitrary geometries. A double walled cylinder is modeled using commercially available software. The outer shell is modeled as an aluminum cylinder, similar to that of aircraft skins. The inner shell is modeled as a composite material representative of a lightweight, stiff trim panel. Two different inner shell materials are used. The first is representative of current trim structure, the second a much stiffer composite. The primary source is generated by an exterior acoustic monopole. Control fields are generated using normal force inputs to the inner cylindrical shell. A linear least mean square (LMS) algorithm is used to determine amplitudes of control forces that minimize the interior acoustic field. Coupling of acoustic and structural modes and noise reductions are discussed for each of the inner shell materials.

Coats, T. J.↗