Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “direct drive”

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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Machine-Learning-Driven, Site-Specific Weather Forecasting for Grid-Interactive Efficient Buildings: Preprint

Emerging grid-interactive efficient buildings (GEBs) have great potential to provide much-needed demand flexibility to electric grids while fulfilling their own control targets by co-optimizing smart appliances, solar photovoltaics, electric vehicles, and energy storage at buildings. To enable the optimal operation of GEBs, site-specific weather information—such as temperature, solar irradiance, relative humidity, and wind speed—is crucial; however, this information is generally unavailable or expensive to obtain. This paper develops advanced machine learning methods to provide precise weather forecasts for individual building sites using readily available weather station data. Support vector regression and artificial neural networks have been employed to learn the spatiotemporal correlations between the weather conditions at nearby weather stations and the individual building site. The proposed site-specific weather forecasting methods have been validated using 1-year actual weather measurement data collected in the Denver metro area. Results show that the developed machine-learning-driven methods can accurately forecast the temperature at the target building site 1 hour ahead with mean absolute error less than 0.72°C and a 48% improvement over the persistence method. Site-specific weather forecasts will improve the understanding of the microclimate effect and its impact on building energy consumption. This information will drive efficiency upgrades and adjustments of building control strategies to improve energy savings and increase flexibility in building loads.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Evaluating ecosystem water use efficiency under drought stress: a case study of the Helan Mountain region, northwest China

Context Water use efficiency (WUE) is a fundamental ecological indicator links carbon assimilation and water loss in terrestrial ecosystems. Understanding its responses to drought stress is essential for adaptive ecosystem management, particularly in climate-sensitive mountain landscapes. Objectives This study aimed to investigate drought-driven variations in WUE across major vegetation types in the Helan Mountain region of Northwest China. Specifically, we sought to identify dominant ecological drivers of WUE variability and to disentangle their relative importance and causal pathways. Methods We quantified WUE using the Moderate Resolution Imaging Spectroradiometer (MODIS) products and the Drought Severity Index (DSI) data from 2001 to 2020. To examine WUE – drought relationships across contrasting vegetation types, we employed a spatially explicit analytical framework integrating Random Forest (RF) modeling, partial correlation analysis, and structural equation modeling (SEM). Results Regional WUE exhibited relatively stable interannual dynamics, yet pronounced spatial heterogeneity that was strongly modulated by drought conditions. Vegetation properties, particularly Leaf Area Index (LAI) and Normalized Difference Vegetation Index (NDVI), emerged as the dominant determinants of WUE, with NDVI alone explaining over 20% of its spatial variance in forest and grassland during non-drought periods. SEM analyses revealed that climate forcing influenced WUE mainly through indirect pathways mediated by soil moisture availability and vegetation structural dynamics, rather than through direct climatic controls. Among all regulating factors, LAI acted as the central control node governing ecosystem carbon–water coupling. In contrast, short-term climatic stress, especially atmospheric demand and drought duration, exerted weak or negative direct effects on WUE. Ecosystem-specific responses were observed, with croplands mainly regulated by soil water availability, whereas forests and grasslands showed more sensitive to atmospheric drought stress. Together, these results reveal a hierarchical control framework where soil–vegetation interactions mediate climate impacts on WUE, driving strong spatial heterogeneity in drought responses across mountain landscapes. Conclusions Our findings highlight the pivotal role of indirect drought effects mediated by vegetation and soil processes in shaping ecosystem WUE. The identified soil–vegetation–climate regulatory hierarchy provides mechanistic insight into landscape–scale drought sensitivity and supports integrated modeling approaches for evaluating ecosystem resilience and sustainable management in arid mountain regions.

China↗
DOE OSTI2021

Discrete stochastic model of point defect-dislocation interaction for simulating dislocation climb

Dislocation climb is an important high temperature process in metals plasticity, responsible for the phenomena such as creep, swelling, or hardening. Climb is defined by the ability of dislocations to leave their original glide plane by interacting with point defects. As such, dislocation climb is controlled by point defect diffusion/absorption/emission, all of which involve thermal activation. The existing thermodynamically consistent models for climb are generally formulated in a continuum framework, through the definition of effective defect fluxes and climb propensities in response to thermodynamic driving forces. However, the point-wise discrete nature of vacancies (and/or self-interstitials) confers a highly discrete nature to the climb dynamics, which is also strongly affected by elastic forces. The combination of discreteness, thermal activation, and elasticity makes this process too challenging for direct atomistic methods such as molecular dynamics. Here we develop a kinetic Monte Carlo model that captures vacancy generation and transport kinetics acting in conjuction with the evolving elastic fields provided by discrete dislocation dynamics simulations. The two models are coupled via the applied stresses and stress gradients generated by dislocation structures at vacancy locations. Our simulations reveal two surprising results. First that climb is dominated by vacancy emission even when the background vacancy concentration is much higher than the equilibrium one. And, second, that climb velocities might be much faster than otherwise believed when one uses the classical theories of climb. These effects are due to the locality of vacancy-dislocation processes, which are not captured in classical treatments that assume smooth vacancy fluxes and homogeneous concentrations. We apply the method to study elementary climb processes in body-centered cubic iron and furnish climb mobility functions to be used in parametric dislocation dynamics and/or crystal plasticity simulations. Here, we apply the technique to study non-conservative plastic bypass of spherical precipitates by edge dislocations and point out the differences between our discrete approach and existing continuum formulations.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Structure-based design of a strain transcending AMA1-RON2L malaria vaccine

Apical membrane antigen 1 (AMA1) is a key malaria vaccine candidate and target of neutralizing antibodies. AMA1 binds to a loop in rhoptry neck protein 2 (RON2L) to form the moving junction during parasite invasion of host cells, and this complex is conserved among apicomplexan parasites. AMA1-RON2L complex immunization achieves higher growth inhibitory activity than AMA1 alone and protects mice against Plasmodium yoelii challenge. Here, three single-component AMA1-RON2L immunogens were designed that retain the structure of the two-component AMA1-RON2L complex: one structure-based design (SBD1) and two insertion fusions. All immunogens elicited high antibody titers with potent growth inhibitory activity, yet these antibodies did not block RON2L binding to AMA1. The SBD1 immunogen induced significantly more potent strain-transcending neutralizing antibody responses against diverse strains of Plasmodium falciparum than AMA1 or AMA1-RON2L complex vaccination. This indicates that SBD1 directs neutralizing antibody responses to strain-transcending epitopes in AMA1 that are independent of RON2L binding. This work underscores the importance of neutralization mechanisms that are distinct from RON2 blockade. The stable single-component SBD1 immunogen elicits potent strain-transcending protection that may drive the development of next-generation vaccines for improved malaria and apicomplexan parasite control.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Model for current drive induced crash cycles in W7-X

In the Wendelstein 7-X (W7-X) stellarator, the vacuum rotational transform, ι, has a flat radial profile and does not cross any major rational resonance. Nevertheless, during plasma operation the ι–profile can be strongly modified by electron cyclotron current drive in such a way that the resulting ι-profile passes through low-order rational values, and this can trigger magnetohydrodynamic (MHD) events. Indeed, W7-X plasmas are sometimes subject to repetitive collapses of core confinement, which can be observed regardless of the direction in which the EC current is driven. Even though the origin of these MHD instabilities is under investigation, the crashes may be connected to the formation of magnetic islands and magnetic reconnection. In the present work, we try to shed light on the dynamics of different events happening during the course of sawtooth cycles in W7-X by proposing a model that combines a slow current diffusion with a recipe for fast relaxation that conserves the corresponding helical flux (Kadomtsev 1975 Fiz. Plazmy 1 710–15). We also propose a simple model based on Taylor relaxation (Taylor 1974 Phys. Rev. Lett. 33 1139), (Taylor 1986 Rev. Mod. Phys. 58 741) to predict the nonlinear redistribution of plasma current caused by the largest of the observed events.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Pressure Barrier Applicability to Polymer Flood Design

Effective oil displacement from a reservoir requires adequate and properly directed pressure gradients in areas of high oil saturation. If the polymer bank is too large or too viscous during a polymer flood, the pressure drop from the injection well to the polymer front may act as a pressure barrier by usurping most of the downstream driving force for oil displacement. Polymer injection pressures must be limited. The maximum allowable injection pressure is commonly constrained by caprock integrity, injection equipment, and/or regulations, even though fractures can be beneficial to polymer injectivity (and even sweep efficiency in some cases). This paper examines when the pressure-barrier concept limits the size and viscosity of the polymer bank during a polymer flood. Both analytical and numerical methods are used to address this issue. We examine the relevance of the pressure barrier concept for a wide variety of circumstances, including oil viscosities ranging from 10-cp (like at Daqing, China) to 1650-cp (like at Pelican Lake, Alberta), vertical wells (like at Tambaredjo, Suriname) versus horizontal wells (like at Milne Point, Alaska), single versus multiple layered reservoirs, permeability contrast, and with versus with crossflow between layers. We also examine the relation between the pressure-barrier concept and fractures and fracture extension during polymer injection. We demonstrate that in reservoirs with single layers, the pressure-barrier concept only limits the optimum viscosity of the injected polymer if the mobility of the polymer bank is less than the mobility of the displaced oil bank. The same is true for multi-zoned reservoirs with no crossflow between layers. Thus, for these cases, the optimum polymer viscosity is likely to be dictated by the mobility of the oil bank, unless other factors (like fracture extension) intervene. For multi-zoned reservoirs with free crossflow between layers, the situation is different. A compromise must be reached between injected polymer viscosity and the efficiency of oil recovery. The relevance of our findings is applied to operations for several existing polymer floods. This work is particularly relevant to viscous-oil reservoirs (like Pelican Lake and others) where the injected polymer viscosities are substantially lower than the oil viscosity

Wang, Dongmei↗
DOE OSTI2020

Collaborative Research: Natural Organic Matter and Microbial Controls on Mobilization/Immobilization of I and Pu in Soils and Waters Affected by Radionuclide Releases in USA and Japan

In this project, the relationship between natural organic matter (NOM) and two radioactive elements that are relevant to nuclear waste disposal were studied: Plutonium (Pu) and Iodine. The human and environmental risks associated with Pu stem mainly from the very long half-lives of several of its isotopes ( 238 Pu, 88 yr; 239 Pu, 24,100 yr; 240 Pu, 6560 yr) and its radiotoxicity. Understanding Pu biogeochemical behavior in both near-field (>10-11M) and far-field scales (<10-11M) is imperative to the development of approaches for reprocessing Pu, remediation of Pu contamination and accurate assessment of risks posed by disposal practices for Pu-bearing wastes. The environmental mobility of Pu can be affected by redox potential, pH, adsorption, precipitation, complexation, colloid formation, and microbial activity, of which the first characteristic has the most profound influence. Numerous studies have shown high affinity of Pu towards NOM, as well as to mineral phases. NOM is ubiquitous in the environment, e.g., both fulvic and humic acids are able to reduce Pu(V,VI) to Pu(IV) and the redox potential of NOM is positively related to the abundance of phenolic/acidic OH groups. NOM can either facilitate or limit actinide migration, depending on specific biogeochemical conditions including pH, mineral and organic matter characteristics, etc. The other radionuclide of interest is radioiodine ( 129 I). 129I is a major by-product of nuclear fission and of serious concern to the Department of Energy (DOE) as it is among the top risk drivers at existing and potential radiowaste-contaminated sites. The risk of 129 I stems largely from its high bioconcentration factor (90% of the body’s iodine is accumulated in the thyroid), a high inventory at source terms, a very long-half life (16M years), and rapid mobility in the subsurface environment. As a consequence, 129 I has the lowest drinking water standard (1 pCi/L) among all radionuclides in the Federal Register. With a novel and sensitive gas chromatography-mass spectrometry (GC-MS) method developed in our lab, it is possible to quickly and simultaneously determine the distribution of 129 I and stable 127 I forms in environments, as low as 2 pCi/L for 129 I. This method was subsequently validated using accelerator mass spectroscopy, AMS. IO 3 - and organo-I were determined as major species in the groundwater of SRS and the Hanford Site, contrary to thermodynamic predictions that I- should be the dominant species at these sites. Mobility of 129 I was also demonstrated to depend greatly on the I species and its concentration, sediment pH, and redox state, with times to achieve equilibrium taking up to 12 weeks. Along the groundwater pathway in the F-Area of SRS, 129 I- supplied from the seepage basins was transformed to 129 IO 3 - and organo- 129 I with increasing iodine sediment sorption, causing the lower total 127 I and 129 I concentrations along the gradient transect of the waste plume. By contrast, groundwater 129 I concentrations in the wetlands (as high as 1617.3 pCi/L) were greatly elevated with respect to the source term (159.3 pCi/L). While the NOM promoted the uptake of 129 I to the wetland sediment, it also promoted the formation of soluble organic fraction. A small fraction of NOM that is bound to iodine can behave as a mobile organo-I source. Iodide was enzymatically incorporated into NOM, whereas both iodide and iodate were abiotically bound to NOM, under certain conditions. Iodate removal from the mobile aqueous phase can also occur through incorporation into carbonate (e.g., at the Hanford Site, USA). Thus immobilization and re-mobilization of iodine species were influenced by pH, Eh and the presence of NOM and metal oxides, which adds to the complexity of site remediation action. A ground-breaking result was to elucidate the products (i.e. organo-iodine moieties formed via enzymatic and non-enzymatic processes) at the molecular level by nuclear magnetic resonance (NMR) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS). We found that iodine-NOM interactions may be influenced by NOM hydrophobic aliphatic moieties. From the perspective of ESI-FTICRMS, organo-iodine formulas were ascribed to the groups of unsaturated hydrocarbons, lignins and proteins. Iodate is likely abiotically reduced to reactive iodine species by lignin- and tannin-like compounds or carboxylic-rich alicyclic molecules (CRAM). We also investigated microbial mechanisms in iodine incorporation into NOM. We established that soil bacteria isolated from F-Area of SRS did not accumulate significant amounts of I- (0.2-2%). Intracellular uptake of I- decreases with increasing pH when pH ranged from 4 to 6. In contrast, 44 out of 84 strains isolated from the F-Area of SRS can transform I- to IO 3 - and organo-iodine. In some cases, oxidation was facilitated in the presence of H 2 O 2 . Microbes can also excrete organic acids that enhance I- oxidation by lowering the ambient pH and reacting with H 2 O 2 to form peroxy carboxylic acids. At lower pH values (≤5), H 2 O 2 hydrolysis was the driving force for iodide-oxidation; whereas, at pH ≥ 6, spontaneous decomposition of peroxy carboxylic acids, originating from H 2 O 2 and organic acids were the primary cause of iodide oxidation. Lastly, it was determined that microbial processes involved in Mn (II) are capable of directly oxidizing I- via enzymatic catalysis (i.e., multicopper oxidases), or indirectly through the formation of reactive oxygen species (ROS) and/or biogenic manganese oxides. ROS-mediated oxidation of I- was found to predominate at pH >5, whereas the enzymatic and Mn oxide pathways were more active at pH < 5. Together, this project has resulted in 9 publications in high-impact journals, and the training of 1 Ph.D and 4 undergraduate students.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Fuel driven near isothermal compressor

A gas compressor system includes a compression liquid holding tank in fluid communication with a combustion tank. A combustible fluid is directed to the combustion tank. An ignition system is provided for igniting the combustible fluid. A compression liquid flows between the liquid holding tank, the combustion tank, and a compression tank. A compressible gas is provided in the compression tank. The ignition of the combustible fluid drives the compression liquid from the combustion tank to the compression tank, compressing the compressible liquid. An HVAC&R system and a method of compressing gas are also disclosed.

Momen, Ayyoub Mehdizadeh↗
DOE OSTI2024

Towards Energy–Efficient Direct Air Capture with Photochemically–Driven CO 2 Release and Solvent Regeneration

The intensive energy demands associated with solvent regeneration and CO 2 release in current direct air capture (DAC) technologies makes their deployment at the massive scales (GtCO 2 /year) required to positively impact the climate economically unfeasible. This challenge underscores the critical need to develop new DAC processes with significantly reduced energy costs. Recently, we developed a new approach to photochemically drive efficient release of CO 2 through an intermolecular proton transfer reaction by exploiting the unique properties of an indazole metastable-state photoacid (mPAH), opening a new avenue towards energy efficient on-demand CO 2 release and solvent regeneration using abundant solar energy instead of heat. In this Concept Article, we will describe the principle of our photochemically-driven CO 2 release approach for solvent-based DAC systems, discuss the essential prerequisites and conditions to realize this cyclable CO 2 release chemistry under ambient conditions. We outline the key findings of our approach, discuss the latest developments from other research laboratories, detail approaches used to monitor DAC systems in situ, and highlight experimental procedures for validating its feasibility. Finally, we conclude with a summary and outlook into the immediate challenges that must be addressed in order to fully exploit this novel photochemically-driven approach to DAC solvent regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Curvature Induced Modifications of Chirality and Magnetic Configuration in Perpendicular Films

Designing curvature in three-dimensional (3D) magnetic nanostructures enables controlled manipulation of local energy landscapes, allowing for the modification of noncollinear spin textures relevant for next-generation spintronic devices. In this study, we experimentally investigate 3D magnetization textures in a Co/Pd multilayer film, exhibiting strong perpendicular magnetic anisotropy (PMA), deposited onto curved Cu nanowire meshes with diameters as small as 50 nm and lengths of several microns. Utilizing magnetic soft X-ray nanotomography, we achieve reconstructions of 3D magnetic domain patterns at approximately 30 nm spatial resolution. This approach provides detailed information on both the orientation and magnitude of magnetization within the film. Our results reveal that interfacial anisotropy in the Co/Pd multilayers drives the magnetization toward the local surface normal. In contrast to typical labyrinth domains observed in planar films, the presence of curved nanowires significantly alters the domain structure, with domains preferentially aligning along the nanowire axis in close proximity, while adopting random orientations farther away. We report direct experimental observation of a curvature-induced Dzyaloshinskii-Moriya interaction (DMI), which is quantified to be approximately one-third of the intrinsic DMI in Co/Pd stacks. The curvature induced DMI enhances stability of Néel-type domain walls. These experimental observations are further supported by micromagnetic simulations. Altogether, our findings demonstrate that introducing curvature into magnetic nanostructures provides a powerful strategy for tailoring complex magnetic behaviors, paving the way for the design of advanced 3D racetrack memory and neuromorphic computing devices.

Raftrey, David↗
DOE OSTI2023

Spontaneous assembly of hierarchical phases

We report the grand promise of self-assembly is the creation of target nanostructures through spontaneous molecular organization, a process that is — in principle — simpler and more scalable than laborious top-down nanofabrication methods. Yet self-assembly faces a fundamental challenge: the structures that form thermodynamically tend to minimize surface area and maximize symmetry; the most readily-accessible structures are thus quite simple. Block copolymer (BCP) self-assembly, for example, takes advantage of the chemical incompatibility along a polymer backbone to drive local phase separation; frustrated assembly leads to a nanoscale morphology whose unit cell is dictated by chain architecture. Canonical BCPs (linear chains with two blocks) form alternating lamellae and hexagonally-packed cylinders in a straightforward manner; but more exotic phases require additional control, for example directing the assembly using external forces, such as shear or chemical templates. An elegant alternative is to use synthetic methods to design more sophisticated chain architectures, which may give rise to new morphologies. An outstanding challenge is to achieve morphological control without undue synthetic burden. Sun et al. now report in Nature Nanotechnology the design and synthesis of novel triblock copolymers that give rise to structural order at multiple length scales, thereby forming complex and hierarchical nanoscale phases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Aqueous-soluble bipyridine cobalt($\tiny{II}$/$\tiny{III}$) complexes act as direct redox mediators in photosystem I-based biophotovoltaic devices

Sustainable energy production is critical for meeting growing worldwide energy demands. Due to its stability and reduction potential, photosystem I (PSI) is attractive as the photosensitizer in biophotovoltaic devices. Herein, we characterize aqueous and organic solvent soluble synthetic bipyridine-based cobalt complexes as redox mediators for PSI-based biophotovoltaics applications. Cobalt-based complexes are not destructive to protein and have appropriate midpoint potentials for electron donation to PSI. We report on PSI stability in organic solvents commonly used in biophotovoltaics. We also show the effects of a mixed organic solvent phase on PSI reduction kinetics, slowing reduction rates approximately 8–38 fold as compared to fully aqueous systems, with implications for dye regeneration rates in PSI-based biophotovoltaics. Further, we show evidence of direct electron transfer from cobalt complexes to PSI. Finally, we report on photocurrent generation from Co mediator-PSI biophotovoltaic devices. Taken together, we discuss the development of novel Co complexes and our ability to fine-tune their characteristics via functional groups and counteranion choice to drive interaction with a biological electron acceptor on multiple levels from redox midpoints, spectral overlap, and solvent requirements, among others. This work suggests that fine-tuning of redox active species for interaction with a biological partner is possible for the creation and improvement of low cost, carbon-neutral energy production in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Magnetic reconnection and kinetic waves generated in the Earth's quasi-parallel bow shock

Magnetic reconnection in quasi-parallel shocks, relevant to the Earth’s bow shock, is studied by means of two-dimensional full particle-in-cell simulations. As the Alfvénic Mach number increases, the propagation direction of the waves excited in the transition region changes, and the shock becomes more turbulent with more reconnection sites. In the higher Mach number shock, abundant electron-only reconnection sites are generated with scales on the order of the ion skin depth or less. Non-reconnecting current sheets can also generate electron jets and energy dissipation can occur there as well. However, non-reconnecting current sheets with the magnetic field reversal typically show a smaller energy dissipation rate than reconnecting current sheets. In the shock transition region, two types of waves are responsible for driving reconnection: one has a wavelength around three ion skin depths (d i ), and the other has a wavelength less than 1 d i . Here, electron and ion distribution functions show that in regions where the former type of waves is excited, there are two ion beams and a single-peaked electron distribution. In contrast, in regions where the latter type of waves is excited, there are multiple electron and ion beams. The waves propagating obliquely to the magnetic field bend the magnetic field lines, and magnetic reconnection occurs where oppositely directed field lines come into contact.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Double cylinder implosion experiments at the National Ignition Facility

Here, cylindrical implosion experiments are used to directly measure instability growth in a convergent geometry, providing a wealth of data for model validation. Double cylinders are a natural extension of the platform and enable measurements at a classically unstable interface, the outer surface of the inner cylinder, which experiences no ablative stabilization from the laser drive. However, the utility of this platform relies upon maintaining adequate axial uniformity of the inner cylinder during the implosion. Although previous smaller-scale double cylinder experiments exhibited acceptable levels of axial uniformity, radiation-hydrodynamics simulations of larger-scale double cylinders predict more axial non-uniformity induced by the impedance mismatch as the shock wraps around the axial ends of the inner cylinder. A mechanism to reduce axial non-uniformity in these larger double cylinder implosions is presented, and preliminary experimental data confirms the efficacy of the selected mitigation approach.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Design tool for estimating metal hydride storage system characteristics for light-duty hydrogen fuel cell vehicles

The U.S. Department of Energy (DOE) has developed the Framework model to simulate fuel cell-based light-duty vehicle operation for various hydrogen storage systems. This transient model simulates the performance of the storage system, fuel cell, and vehicle for comparison to DOE's Technical Targets using four drive cycles. Metal hydride hydrogen storage models have been developed for the Framework model. Despite the utility of this model, it requires that material researchers input system design specifications that cannot be easily estimated. To confront this challenge, a design tool has been developed that allows researchers to directly enter physical and thermodynamic metal hydride properties into a simple sizing module that then estimates the systems parameters required to run the storage system model. This design tool can also be used as a standalone MS Excel model to estimate the storage system mass and volume outside of Framework and compare it to the DOE Technical Targets. This model will be explained and exercised with existing hydrogen storage materials.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Bridging the Void: Halogen Bonding and Aromatic Interactions to Program Luminescence and Electronic Properties of π -Conjugated Materials in the Solid State

π-Conjugated materials are promising candidates for emerging organic optoelectronic devices empowered by molecular design. The unsolved challenges of predicting and controlling their packing as solids, central to their properties and performance, currently limits their practical application. As noncovalent interactions drive packing, control over such interactions are critical to bridging from chemical structure to functional properties. In molecular crystals, halogen bonding and interactions of aromatic rings have emerged as versatile tools for noncovalent control with tailored luminescence and electronic properties. Here, we describe how the interplay of these directional and tunable interactions can engineer properties, including stimuli-responsive behavior. Specifically, halogen bonding can provide robust designs for directing 2D molecular assembly, whereas the intentional interactions of aromatic rings can yield metastable, switchable packing modes, as well as programmed stacking between layers of chromophores. Examples, herein, demonstrate clear relationships between assembly by design and resulting solid-state properties, and strategies presented offer guidance for future designs of π-conjugated molecular materials using specific aromatic interactions and halogen bonding.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Immobilizing a Lehn-Type Catalyst with Nitrocyclocondensation Chemistries: CO 2 Reduction on Silicon Hybrid Photoelectrodes

Here, we present the first examples of installing a redox reporter and CO 2 reduction (CO 2 R) catalyst onto freshly HF-etched Si (photo)­electrodes using a solution-phase nitrocyclocondensation (NCC) reaction. Previous studies detailed the mechanism of NCC reactions on Si under ultrahigh vacuum conditions but have not applied these chemistries to generate functional (photo)­electrodes. Installing 4-nitrophenyl ferrocene (4-NpFc) molecules directly onto degenerately doped p + Si allowed us to evaluate the effects of different NCC reaction conditions on coverage (e.g., 3.6 ± 1.2 × 10 –11 mol/cm 2 ) and electrochemical reversibility. The 4-NpFc molecules remained immobilized under the reducing potentials (−2.0 V vs Fc +/0 in acetonitrile) needed to drive molecular CO 2 R catalysts. Installing 4-nitroaniline (4-NA) molecules onto low-doped pSi allowed us to couple Lehn-type Re­(I) catalysts with pendant carboxylic acids. The CO Faradaic efficiency of CO production under 1-sun illumination (−2.15 V vs Fc +/0 ) was 23% in CO 2 -saturated electrolyte, a value that surpasses previous examples of CO 2 R catalyst monolayers on Si. These two examples highlight the versatility of solution-phase NCC attachment chemistries for generating functional Si (photo)­electrodes.

catalysis↗
DOE OSTI2022

Pressure Modification or Barrier Issues during Polymer Flooding Enhanced Oil Recovery

Effective oil displacement from a reservoir requires adequate and properly directed pressure gradients in areas of high oil saturation. If the polymer bank is too large or too viscous during a polymer flood, the pressure drops from the injection well to the polymer front may act as a pressure modification or barrier by usurping most of the downstream driving force for oil displacement. Polymer injection pressures must be limited. The maximum allowable injection pressure is commonly constrained by caprock integrity, injection equipment, and/or regulations, even though fractures can be beneficial to polymer injectivity. This paper examines when the pressure-barrier concept limits the size and viscosity of the polymer bank during a polymer flood. Analytical and numerical methods are used to address this issue. We examine the relevance of the pressure modification concept for a wide variety of circumstances, including oil viscosities ranging from 10 cp to 1650 cp, vertical wells versus horizontal wells, single versus multiple layered reservoirs, permeability contrast, and crossflow between layers. We also examine the relation between the pressure-barrier concept and fractures and fracture extension during polymer injection. We demonstrate that in reservoirs with single layers, the pressure-barrier concept only limits the optimum viscosity of the injected polymer if the mobility of the polymer bank is less than the mobility of the displaced oil bank. The same is true for multizoned reservoirs with no crossflow between layers. Thus, for these cases, the optimum polymer viscosity is likely to be dictated by the mobility of the oil bank, unless other factors intervene. For multizoned reservoirs with free crossflow between layers, the situation is different. A compromise must be reached between injected polymer viscosity and the efficiency of oil recovery. This work is particularly relevant to viscous oil reservoirs where polymer viscosities are substantially lower than the oil viscosity.

58 GEOSCIENCES↗