Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Splitting”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

The basis for reevaluating the reactivity of pyrite surfaces: spin states and crystal field d-orbital splitting energies of bulk, terrace, edge, and corner Fe( II ) ions

Pyrite, one of the most important minerals to catalyze redox reactions in nature and a bulk low-spin Fe mineral, needs to provide high-spin Fe on surfaces to moderate spin-forbidden transitions. In this work, the spin state of pyrite is investigated using density functional theory (DFT) calculations on cluster and periodic models. The energies of clusters Fe x S 2 x (where x = 4, 8, 16, and 32) were calculated as a function of total spin and different up/down spin configurations. The undercoordinated Fe on surfaces, edges, and corners were found to provide intermediate and high-spin Fe necessary for catalysis. Generally, the lower the crystal field splitting energy (CFSE), Δ, for a particular Fe atom, the higher is the spin density. Pyrite bulk (3D) and surfaces (2D) (+ water to mimic aqueous systems) were examined. The calculated bulk band gap (0.95 eV) is in excellent agreement with previous reports. For the surface, a conducting state is predicted. The calculated CFSE for bulk Fe( II ) in pyrite (~2.2 eV) agrees with previous CFT results; due to surface states, this CFSE decreases to ~1 eV on terraces. This study highlights the importance of accurately describing the spin state of pyrite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Transition-metal single atoms in nitrogen-doped graphenes as efficient active centers for water splitting: a theoretical study

Highly active single-atom catalysts (SACs) have recently been intensively studied for their potential in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Due to the existence of many such SAC systems, a general understanding of the trend and designing principle is necessary to discover an optimal SAC system. In this work, by using density functional theory (DFT), we investigated a series of late single transition metals (TM = Fe, Co, Ni, Cu, and Pd) anchored on various N doped graphenes (xN–TM, x = 1–4) as electrocatalysts for both the HER and OER. Solvent effects were taken into account using an implicit continuum model. Our results reveal that the catalytic activity of SACs is determined by the local coordination number of N and TM in the catalysts. Among the considered catalysts, a low-coordinated Co site, i.e. a triple-coordinated Co, exhibits a high catalytic activity toward the HER with a calculated hydrogen adsorption free energy of –0.01 eV, whereas a high-coordinated Co center, i.e. a quadruple-coordinated Co is a promising candidate for the OER with a low computed overpotential of –0.39 V, which are comparable to those of noble metal catalysts, indicating superior HER and OER performance of N–Co co-doped graphenes. The results shed light on the potential applications of TM and N co-doped graphenes as efficient single-atom bifunctional catalysts for water splitting, thereby functioning as promising candidates for hydrogen/oxygen production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Progress on ternary oxide-based photoanodes for use in photoelectrochemical cells for solar water splitting

Solar water splitting using photoelectrochemical cells (PECs) has emerged as one of the most promising routes to produce hydrogen as a clean and renewable fuel source. Among various semiconductors that have been considered as photoelectrodes for use in PECs, oxide-based photoanodes are particularly attractive because of their stability in aqueous media in addition to inexpensive and facile processing compared to other types of semiconductors. However, they typically suffer from poor charge carrier separation and transport. In the past few years, there has been tremendous progress in developing ternary oxide-based photoelectrodes, specifically, photoanodes. The use of ternary oxides provides more opportunities to tune the composition and electronic structure of the photoelectrode compared to binary oxides, thus providing more freedom to tune the photoelectrochemical properties. In this article, we outline the important characteristics to analyze when evaluating photoanodes and review the major recent progress made on the development of ternary oxide-based photoanodes. For each system, we highlight the favorable and unfavorable features and summarize the strategies utilized to address the challenges associated with each material. Finally, by combining our analyses of all the photoanodes surveyed in this review, we provide possible future research directions for each compound and an outlook for constructing more efficient oxide-based PECs. Overall, this review will provide a critical overview of current ternary oxide-based photoanodes and will serve as a platform for the design of future oxide-based PECs.

25 ENERGY STORAGE↗
DOE OSTI2019

New aspects of improving the performance of WO 3 thin films for photoelectrochemical water splitting by tuning the ultrathin depletion region

In this paper, we explored a facile, scalable and effective method for substantially enhancing photocurrent and incident-photon-to-current efficiency of WO 3 thin-film photoanodes by a mild reduction treatment under low oxygen pressure. Experimental data from photoelectrochemical and electrochemical impedance spectroscopies have shown that such treatment can increase the charge carrier density on WO 3 photoanode surfaces resulting in improvements in hole collection efficiency and reduction in charge recombination. Despite a much thinner layer of WO 3 (about 500 nm) compared to those in other published studies, the electrodes exhibited an ultra-high photocurrent density of 1.81 mA cm –2 at 1.23 V vs . RHE. This current density is one of the highest ones among WO 3 -based photoanodes described in literature. As a result, the proposed surface modulation approach offers an effective and scalable method to prepare high-performance thin film photoanodes for photoelectrochemical water splitting.

36 MATERIALS SCIENCE↗
DOE OSTI2019

On the active site for electrocatalytic water splitting on late transition metals embedded in graphene

Transition-metal atoms embedded in nitrogen-doped graphene can be used for electrocatalytic water splitting, but there are open questions regarding the identity of the active site. We study the formation of hydrogen and oxygen as well as the reduction of oxygen on 14 transition metals embedded in nitrogen-doped graphene using density functional theory and find that the stability and the catalytic properties of the metals depend on the nitrogen content of the support. While previous studies focus on metal atoms inside nitrogen-free and fully substituted vacancies, we find that partially nitrogen-substituted single sites are significantly more active for later transition metals (groups 10–11). These sites are also more stable than previously suggested active-site models. Our findings suggest that stability and catalytic activity of late transition metals embedded in graphene could be increased by controlling the nitrogen content of the support to obtain partially substituted vacancy sites. For early transition metals, fully substituted vacancies represent the most active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Strain stabilized nickel hydroxide nanoribbons for efficient water splitting

Development of efficient and durable oxygen evolution reaction (OER) catalysts has a direct impact on water splitting efficiency and cost effectiveness. In this work, we report the successful synthesis of a new Ni(OH) 2 structure, strain-stabilized Ni(OH) 2 nanoribbons (NR-Ni(OH) 2 ) two to three layers thick, with widths of 2-5 nm, via an electro-oxidation route. Conventional Ni(OH) 2 usually has negligible OER activity, while NR-Ni(OH) 2 shows a high activity for the oxygen evolution reaction, an overpotential of 162 millivolts and furthermore exhibits long-term stability in alkaline electrolyte. The substantial reduction in overpotential of NR-Ni(OH) 2 is due to its easier OOH* adsorption by the active four-coordinated Ni edge sites. The enhanced catalytic activity of NR-Ni(OH) 2 makes it an excellent candidate for industrial applications.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Tungsten oxide nanostructures and nanocomposites for photoelectrochemical water splitting

Hydrogen production from photoelectrochemical (PEC) water splitting using semiconductor photocatalysts has attracted great attention to realize clean and renewable energy from solar energy. The visible light response of WO 3 with a long hole diffusion length (~150 nm) and good electron mobility (~12 cm 2 V –1 s –1 ) makes it suitable as the photoanode. Yet, WO 3 suffers from issues including rapid recombination of photoexcited electron–hole pairs, photo-corrosion during the photocatalytic process due to the formation of peroxo-species, sluggish kinetics of photogenerated holes, and slow charge transfer at the semiconductor/electrolyte interface. Our report highlights the approaches to overcome these drawbacks of WO 3 photoanodes, including: (i) the manipulation of nanostructured WO 3 photoanodes to decrease the nanoparticle size to promote hole migration to the WO 3 /electrolyte interface which benefits the charge separation; (ii) doping or introducing oxygen vacancies to improve electrical conductivity; exposing high energy crystal surfaces to promote the consumption of photogenerated holes on the high-active crystal face, thereby suppressing the recombination of photogenerated electrons and holes; (iii) decorating with co-catalysts to reduce the overpotential which inhibits the formation of peroxo-species; (iv) other methods such as coupling with narrow band semiconductors to accelerate the charge separation and controlling the crystal phase via annealing to reduce defects. These methods are reviewed with detailed examples.

08 HYDROGEN↗
DOE OSTI2020

Mixed conductive composites for ‘Low-Temperature’ thermo-chemical CO 2 splitting and syngas generation

An effective strategy to design platinum group metal (PGM) free redox catalysts for “low temperature” CO 2 splitting followed with methane partial oxidation was proposed and validated. Composites of mixed ionic-electronic conductive (MIEC) oxides were found to be highly effective at relatively low temperatures (600–750 °C). Specifically, perovskite structured LaNi 0.35 Fe 0.65 O 3 and rock salt structured Ce 0.85 Gd 0.1 Cu 0.05 O 2–δ , as two compatible yet structurally distinct MIEC oxides, were integrated into composite redox catalyst particles. Resulting from the synergistic effect of the two MIEC phases, 90% CO 2 to CO conversion was demonstrated at 750 °C. Up to 90% methane conversion with 96% CO selectivity was also achieved in the methane POx step. The redox catalysts were characterized in detail to illustrate the underlying mechanisms for the synergistic effects. Electrical conductivity relaxation (ECR) measurements indicated significantly lowered activation energy for lattice oxygen (O 2– ) migration (0.43 eV). The enhanced oxygen migration in turn led to reversible exsolution of active transition metal nanoparticles (Ni–Fe alloy) from the mixed oxide, serving as active sites for methane activation while further enhancing lattice oxygen exchange, as confirmed by in situ X-ray diffraction and transmission electron microscopy. In conclusion, the composite redox catalysts demonstrate superior redox activity, coke resistance, and long term redox stability, making them potentially suitable for CO 2 utilization and methane partial oxidation under a hybrid redox process scheme.

03 NATURAL GAS↗
DOE OSTI2025

A new quinoline-based cobalt( II ) catalyst capable of bifunctional water splitting

We report on a new water-soluble cobalt( II ) complex capable of water splitting bifunctionality, i.e., water reduction and water oxidation. The species [Co II (L Qpy )H 2 O]ClO 4 (1), where L Qpy is the deprotonated form of the new tripodal ligand N 1 ,N 1 -bis(pyridin-2-ylmethyl)-N 2 -(quinolin-8-yl)benzene-1,2-diamine, HL Qpy , was developed aiming to replace an oxidation prone methylene group by a sturdy and redox stable quinoline. The molecular and electronic structures of 1 were evaluated by multiple spectroscopic, spectrometric, electrochemical and computational methods, and detailed pre- and post-catalytic studies were conducted to ascertain the molecular nature of the conversions. Complex 1 performs water reduction at a low onset overpotential (η) of 0.65 V at pH 7, reaching TON 3h 2900 (TOF 970 h −1 ) and TON 18h 12 100 (TOF 672 h −1 ) with up to 98% faradaic efficiency (FE). Species 1 also promotes water oxidation at η = 0.34 V under pH 8, achieving TON 3h 193 (TOF 64 h −1 ) at 84% FE. Experimental and DFT results enabled us to propose reaction intermediates and mechanisms.

Lucecki, Carlos A. [Wayne State University, Detroi↗
DOE OSTI2019

A THz driven split-ring resonator based ultrafast relativistic electron streak camera

The use of sub-wavelength metal structures to locally enhance high frequency electromagnetic fields, generally known as plasmonics, enables breakthrough opportunities across diverse fields of research such as nonlinear optics, biosensing, photovoltaics and others. Here we study the application of sub-wavelength metallic resonators tuned in the THz frequency range for manipulation and diagnostics of relativistic electron beams. In this work, we report on the use of a double-sided split-ring structure driven by a near single cycle THz field generated by optical rectification to impart a time-dependent angular deviation (streak) on a 4.5 MeV electron beam. Electrons passing through the small gap reveal field enhancement factors larger than 10, in good agreement with finite difference time domain simulations. This work paves the way for further application of high frequency metallic structures in compact particle accelerators such as for THz-based relativistic electron streaking at fs and sub-fs temporal resolution.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Split-well direct-phonon terahertz quantum cascade lasers

We introduce a so-called “split-well direct-phonon” active region design for terahertz quantum cascade lasers (THz-QCLs). Lasers based on this scheme profit from both elimination of high-lying parasitic bound states and resonant-depopulation of the lower laser level. Negative differential resistance is observed at room temperature, which indicates that each module behaves as a clean 3-level system. This study further uses this design to investigate the impact of temperature on the dephasing time of GaAs/AlGaAs THz-QCLs.

47 OTHER INSTRUMENTATION↗
DOE OSTI2019

Quantum dots with split enhancement gate tunnel barrier control

We introduce a silicon metal-oxide-semiconductor quantum dot architecture based on a single polysilicon gate stack. The elementary structure consists of two enhancement gates separated spatially by a gap, one gate forming a reservoir and the other a quantum dot. We demonstrate, in three devices based on two different versions of this elementary structure, that a wide range of tunnel rates is attainable while maintaining single-electron occupation. A characteristic change in slope of the charge transitions as a function of the reservoir gate voltage, attributed to screening from charges in the reservoir, is observed in all devices, and is expected to play a role in the sizable tuning orthogonality of the split enhancement gate structure. The all-silicon process is expected to minimize strain gradients from electrode thermal mismatch, while the single gate layer should avoid issues related to overlayers (e.g., additional dielectric charge noise) and help improve yield. Finally, reservoir gate control of the tunnel barrier has implications for initialization, manipulation and readout schemes in multi-quantum dot architectures.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Structural tuning of nonlinear terahertz metamaterials using broadside coupled split ring resonators

We present an experimental and numerical study of a terahertz metamaterial with a nonlinear response that is controllable via the relative structural arrangement of two stacked split ring resonator arrays. The first array is fabricated on an n-doped GaAs substrate, and the second array is fabricated vertically above the first using a polyimide spacer layer. Due to GaAs carrier dynamics, the on-resonance terahertz transmission at 0.4 THz varies in a nonlinear manner with incident terahertz power. The second resonator layer dampens this nonlinear response. In samples where the two layers are aligned, the resonance disappears, and the total nonlinear modulation of the on-resonance transmission decreases. The nonlinear modulation is restored in samples where an alignment offset is imposed between the two resonator arrays. Structurally tunable metamaterials and metasurfaces can therefore act as a design template for tunable nonlinear THz devices by controlling the coupling of confined electric fields to nonlinear phenomena in a complex material substrate or inclusion.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Cation-size mismatch as a predictive descriptor for structural distortion, configurational disorder, and valence-band splitting in II-IV-N2 semiconductors

The II-IV-N2 class of heterovalent ternary nitrides has gained significant interest as alternatives to the III-nitrides for electronic and optoelectronic applications. In this study, we apply first-principles calculations based on density functional theory to systematically investigate the effects of structural distortions due to cation size mismatch on the configurational disorder of the cation sublattice and the valence band structure in this class of materials. We find that larger size mismatch between the group-II and the group-IV cations results in stronger lattice distortions from the ideal hexagonal ratio, which in turn inhibits the propensity of these materials toward octet-rule violating cation disorder. We also demonstrate that the formation energy of a single cation antisite pair, which is fast and simple to calculate, is a strong indicator of a material's propensity toward disorder. Furthermore, the breaking of in-plane symmetry leads to a splitting of the top three valence bands at Γ, which is also directly related to the magnitude of structural distortions. Our work demonstrates that the structural and functional properties of the II-IV-N2 materials can be finely tuned through controllable structural distortions that stem from the choice of cations.

Kute, Malhar (ORCID:0000000214364564)↗
DOE OSTI2021

Time evolution of ML-MCTDH wavefunctions. II. Application of the projector splitting integrator

The multi-layer multi-configuration time-dependent Hartree (ML-MCTDH) approach can suffer from numerical instabilities whenever the wavefunction is weakly entangled. These instabilities arise from singularities in the equations of motion (EOMs) and necessitate the use of regularization of the EOMs. The Projector Splitting Integrator (PSI) has previously been presented as an approach for evolving ML-MCTDH wavefunctions that is free of singularities. Here, we will discuss the implementation of the multi-layer PSI with a particular focus on how the steps required relate to those required to implement standard ML-MCTDH. We demonstrate the efficiency and stability of the PSI for large ML-MCTDH wavefunctions containing up to hundreds of thousands of nodes by considering a series of spin-boson models with up to 106 bath modes and find that for these problems, the PSI requires roughly 3–4 orders of magnitude fewer Hamiltonian evaluations and 2–3 orders of magnitude fewer Hamiltonian applications than standard ML-MCTDH and 2–3/1–2 orders of magnitude fewer evaluations/applications than approaches that use improved regularization schemes. Finally, we consider a series of significantly more challenging multi-spin-boson models that require much larger numbers of single-particle functions with wavefunctions containing up to ~1.3×10 9 parameters to obtain accurate dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Direct imaging of shock wave splitting in diamond at Mbar pressure

Understanding the behavior of matter at extreme pressures of the order of a megabar (Mbar) is essential to gain insight into various physical phenomena at macroscales—the formation of planets, young stars, and the cores of super-Earths, and at microscales—damage to ceramic materials and high-pressure plastic transformation and phase transitions in solids. Under dynamic compression of solids up to Mbar pressures, even a solid with high strength exhibits plastic properties, causing the induced shock wave to split in two: an elastic precursor and a plastic shock wave. This phenomenon is described by theoretical models based on indirect measurements of material response. The advent of x-ray free-electron lasers (XFELs) has made it possible to use their ultrashort pulses for direct observations of the propagation of shock waves in solid materials by the method of phase-contrast radiography. However, there is still a lack of comprehensive data for verification of theoretical models of different solids. Here, we present the results of an experiment in which the evolution of the coupled elastic–plastic wave structure in diamond was directly observed and studied with submicrometer spatial resolution, using the unique capabilities of the x-ray free-electron laser (XFEL). The direct measurements allowed, for the first time, the fitting and validation of the 2D failure model for diamond in the range of several Mbar. Our experimental approach opens new possibilities for the direct verification and construction of equations of state of matter in the ultra-high-stress range, which are relevant to solving a variety of problems in high-energy-density physics.

36 MATERIALS SCIENCE↗