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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 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Protein expression, characterization and activity comparisons of wild type and mutant DUSP5 proteins

Background: The mitogen-activated protein kinases (MAPKs) pathway is critical for cellular signaling, and proteins such as phosphatases that regulate this pathway are important for normal tissue development. Based on our previous work on dual specificity phosphatase-5 (DUSP5), and its role in embryonic vascular development and disease, we hypothesized that mutations in DUSP5 will affect its function. Results: In this study, we tested this hypothesis by generating full-length glutathione-S-transferase-tagged DUSP5 and serine 147 proline mutant (S147P) proteins from bacteria. Light scattering analysis, circular dichroism, enzymatic assays and molecular modeling approaches have been performed to extensively characterize the protein form and function. We demonstrate that both proteins are active and, interestingly, the S147P protein is hypoactive as compared to the DUSP5 WT protein in two distinct biochemical substrate assays. Furthermore, due to the novel positioning of the S147P mutation, we utilize computational modeling to reconstruct full-length DUSP5 and S147P to predict a possible mechanism for the reduced activity of S147P. Conclusion: Taken together, this is the first evidence of the generation and characterization of an active, full-length, mutant DUSP5 protein which will facilitate future structure-function and drug development-based studies.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2016

The “Who” and “How” of Microbial Control over Soil Carbon Dynamics: a Multi-omics, Stable Isotope Probing, and Modeling Approach

Soils are the largest repository of organic carbon (C) in the terrestrial biosphere and represent an important source of CO 2 to the atmosphere, releasing 60-75 Pg C annually through microbial decomposition of organic materials. Microbes are key drivers of C cycling, and exhibit a large range in C use efficiency (CUE). CUE is the substrate C incorporated into biomass per substrate assimilated. While small changes in CUE can have profound effects on soil CO 2 flux, our understanding of the intersection of genomic and abiotic factors driving soil CUE dynamics is still very limited. Our long-term goal is to better predict the fate of soil C by developing mathematical and ecosystem models of SOM decomposition that incorporate a genetic and physiological understanding of CUE. The goal of this work was to define genes, metabolic pathways, and phylogenetic signals associated with microbial CUE for terrestrial microorganisms (bacteria and fungi). Our specific objectives are to: (1) Define genomic markers that indicate how terrestrial bacteria and fungi change CUE in response to environmental drivers of microbial activity; (2) Determine how well genomic markers identified predict CUE in soils; and (3) Improve predictions of soil C by incorporating genomics-informed CUE into ecosystem C models based on genomic features defined in and validated for soil in the course of this work. We address these objectives by coupling multi-omics analyses (genomics, metatranscriptomics) with physiological assays (CUE, enzyme activities) across environmental drivers (substrate quantity/quality, temperature, moisture). We employ a hierarchical approach to incrementally scale from cells to ecosystems, starting with pure cultures of bacteria and fungi, then mock communities in artificial, organic matter-free soil, then finally field soil manipulated to elicit microbial communities differing in community composition and CUE. By focusing on microbial isolates and communities in a temperate forest (Harvard Forest), we leverage a rich context for validating data based on multiple ongoing field, lab and modeling studies of soil C cycling. This research couples two culture collections of fungi and bacteria isolated from the Harvard Forest, along with over a decade of field measurements of CUE and C cycling, and microbial community analyses using metagenomics and metatranscriptomics. Because microbial feedbacks to the environment are regulated at the organismic level, the foundation of this research is the physiology and genomics of CUE among isolates that we have determined to be either dominant in our soil system, sensitive to climate change factors, or both. A series of three experiments using artificial soil, lab incubation of field-collected soil, and a field manipulation is designed to validate potential omics-informed, novel genomic markers to be used as proxies for CUE in models. We test our new understanding of the genetic basis for CUE and its implications for soil C dynamics using the trait-based model DEMENT and the ecosystem models MIIMICS and SCAMPS. All models are modified to simulate SOM decomposition in mineral soils and validated with other temperate forest climate change manipulation studies. By developing mathematical and ecosystem models of SOM decomposition that incorporate a genetic and physiological understanding of CUE, we hope to facilitate more realistic models of SOM decomposition for C cycling in soils.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

SPUTTERED THIN FILMS FOR VERY HIGH POWER, EFFICIENT, AND LOW-COST COMMERCIAL SOFCS

The aim of this project was to leverage the low area specific resistance (ASR) of Redox’s GDC electrolyte-based cell architecture and increase solid oxide fuel cell (SOFC) efficiency (i.e., open circuit voltage, or OCV) without significantly increasing cell resistance. The key to achieving the increased SOFC efficiency is the introduction of a thin sputtered yttria stabilized zirconia (YSZ) electron-blocking layer and a thin sputtered gadolinia doped ceria (GDC) barrier layer on top of the half-cell substrate (i.e., anode and GDC electrolyte). A key initial effort of the project was to improve the quality of the half-cell substrate surface so that any remaining defects were significantly smaller than the desired film thickness. During lab-scale trials, we had to overcome challenges with film cracking during post-sputtering treatments (e.g., thermal anneals) as well as damage to the sputtering targets. After the initial lab-scale trials, the focus shifted toward the use of commercial scale sputtering equipment with a sputtering equipment manufacturer in the microelectronics industry. Using the commercial sputtering equipment, we deposited films with different variations of power, PO2, sputtering time, platen speed, etc. We then determined the combinations of sputtering conditions and post-sputtering treatments that yielded high-quality films without cracks or other significant defects. While thin films were deposited on cells as large as 10 cm by 10 cm, the processing was optimized using 4 cm by 4 cm cells. Cell performance was evaluated in stainless-steel test fixtures between 500 °C and 700 °C with hydrogen fuel fed to the anode and air fed to the cathode. Extensive studies allowed us to determine that modified cathode and cathode contact firing processes were required to achieve theoretical OCV. Moreover, use of the new firing processes resulted in the need for a modified cathode contact to achieve a low ASR. In summary, the project demonstrated the performance of high OCV (1.13 V at 650 °C) from sputtered layers and a low ASR (~0.25 Ohms-cm2 at 650 °C) resulting from a modification of cathode/contact processing and the introduction of alternative contact layers that are sufficient to yield a Gen-1 cell with a maximum power density of approximately 1.2 W/cm2. At an operating voltage of 0.74 V, this would yield a cell power density of ~1.1 W/cm2. While not utilized in this project, a Redox Gen-2 cell has a catalyst-infiltrated porous anode that reduces the ASR by more than 50% from that of the Gen-1 cells used in this project. Therefore, if the sputtered YSZ electron-blocking layer and GDC barrier layer are added to a Gen-2 half cell with a similar increase in OCV to the theoretical value of ~1.13 V at 650 °C, and if the same improvement in ASR (from that demonstrated in this project) is achieved when using the Gen-2 half-cell architecture as a sputtered cell substrate, then the power density at 0.74 Vop could be as high as ~2.6 W/cm2. The impact of such power density gains, while still maintaining high cell efficiency, and thus high system efficiency, is a dramatic decrease in system cost because the stack represents ~30-40% of the SOFC system cost.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Development and Characterization of Electrodes for Surface-Specific Attenuated Total Reflection Two-Dimensional Infrared Spectroelectrochemistry

Electrochemical interfaces still have remaining mysteries surrounding the interfacial region of the electrical double layer, despite being prevalent throughout the energy and water remediation industries. The electrical double layer is where many important dynamic processes such as catalysis and electron transfer occur. The goal of this work is to study the electrical double layer with two-dimensional infrared (2D IR) spectroscopy to experimentally access the details of the structural dynamics of this complex environment. However, there are several experimental challenges to applying 2D IR spectroscopy to this application, such as assuring the surface specificity of the spectrum, optimizing the signal strength while minimizing spectral distortions from dispersion and Fano line shapes, and selecting electrode materials that are both sufficiently IR compatible and conductive. Here we will discuss various considerations when designing 2D IR experiments of electrode interfaces utilizing several substrates and experimental configurations and demonstrate a robust method for 2D IR experiments of electrode interfaces under applied potential that combines nonconducting Si ATR wafers with conductive ITO and thin nanostructured films of plasmonically active Au functionalized with 3-mercapto-2-butanone (MCB). We show that layered electrodes on thin Si ATR wafers with MCB are sensitive to applied potential and that the distortions in the linear and 2D IR spectra are heavily dependent on the morphology of the Au surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Ultrafast non-radiative dynamics of atomically thin MoSe 2

Non-radiative energy dissipation in photoexcited materials and resulting atomic dynamics provide a promising pathway to induce structural phase transitions in two-dimensional materials. However, these dynamics have not been explored in detail thus far because of incomplete understanding of interaction between the electronic and atomic degrees of freedom, and a lack of direct experimental methods to quantify real-time atomic motion and lattice temperature. Here, we explore the ultrafast conversion of photoenergy to lattice vibrations in a model bi-layered semiconductor, molybdenum diselenide, MoSe 2 . Specifically, we characterize sub-picosecond lattice dynamics initiated by the optical excitation of electronic charge carriers in the high electron-hole plasma density regime. Our results focuses on the first ten picosecond dynamics subsequent to photoexcitation before the onset of heat transfer to the substrate, which occurs on a ~100 picosecond time scale. Photoinduced atomic motion is probed by measuring the time dependent Bragg diffraction of a delayed mega-electronvolt femtosecond electron beam. Transient lattice temperatures are characterized through measurement of Bragg peak intensities and calculation of the Debye-Waller factor (DWF). These measurements show a sub-picosecond decay of Bragg diffraction and a correspondingly rapid rise in lattice temperatures. We estimate a high quantum yield for the conversion of excited charge carrier energy to lattice motion under our experimental conditions, indicative of a strong electron-phonon interaction. First principles nonadiabatic quantum molecular dynamics simulations (NAQMD) on electronically excited MoSe 2 bilayers reproduce the observed picosecond-scale increase in lattice temperature and ultrafast conversion of photoenergy to lattice vibrations. Calculation of excited-state phonon dispersion curves suggests that softened vibrational modes in the excited state are involved in efficient and rapid energy transfer between the electronic system and the lattice.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A deubiquitylase with an unusually high-affinity ubiquitin-binding domain from the scrub typhus pathogen Orientia tsutsugamushi

Ubiquitin mediated signaling contributes critically to host cell defenses during pathogen infection. Many pathogens manipulate the ubiquitin system to evade these defenses. Here we characterize a likely effector protein bearing a deubiquitylase (DUB) domain from the obligate intracellular bacterium Orientia tsutsugamushi, the causative agent of scrub typhus. The Ulp1-like DUB prefers ubiquitin substrates over ubiquitin-like proteins and efficiently cleaves polyubiquitin chains of three or more ubiquitins. The co-crystal structure of the DUB (OtDUB) domain with ubiquitin revealed three bound ubiquitins: one engages the S1 site, the second binds an S2 site contributing to chain specificity and the third binds a unique ubiquitin-binding domain (UBD). The UBD modulates OtDUB activity, undergoes a pronounced structural transition upon binding ubiquitin, and binds monoubiquitin with an unprecedented ~5 nM dissociation constant. The characterization and high-resolution structure determination of this enzyme should aid in its development as a drug target to counter Orientia infections.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Freestanding highly defect nitrogen-enriched carbon nanofibers for lithium ion battery thin-film anodes

To spread lithium ion batteries into large-scale energy storage technologies, high ener-gy/power densities and long cycling life of carbon-based anodes must be achieved. This re-quires revolutionary design of the anode’s architectures that can facilitate the fast electronic and ionic transport, as well as accommodate the electrode structural instability. Here we re-port a thin-film electrode design and demonstrate its use in flexible, and large-area carbon-based anode assemblies. The fabrication of electrodes is realized by sputtering a graphite tar-get in the high-purity nitrogen atmosphere, then highly-defect nitrogen-doped carbon nano-fibers are deposited vertically onto copper substrates with a thin film configuration. The high-ly-defect nitrogen-doping enhances the lithium storage and transport, the orientation grown mechanism improves the charge transfer, and the compact configuration makes the high tap density possible. As a result, the thin films exhibit high specific capacities of ~ 500 mAh g-1, namely a volume capacity of ~ 100 mAh cm-3. They also exhibit stable cycle performance (400 mAh g-1 after 200 cycles) and good rate capability (450 mAh g-1 at 1 A g-1 rate). This work opens up a new carbon-based anode design by using sputtering technology for effec-tively incorporating high content nitrogen into carbon matrices. Such electrode architecture significantly improves the electrochemical performance of carbon-based materials.

25 ENERGY STORAGE↗
DOE OSTI2020

High voltage GaN p-n diodes formed by selective area regrowth

GaN p-n diodes were formed by selective area regrowth on freestanding GaN substrates using a dry etch, followed by post-etch surface treatment to reduce etch-induced defects, and subsequent regrowth into wells. Etched-and-regrown diodes with a 150 gm diameter achieved 840 V operation at 0.5 A/cm 2 reverse current leakage and a specific on-resistance of 1.2 mΩ•cm 2 . Etched-and-regrown diodes were compared with planar, regrown diodes without etching on the same wafer. Both types of diodes exhibited similar forward and reverse electrical characteristics, which indicate that etch-induced defectivity of the junction was sufficiently mitigated soas not to be the primary cause for leakage. An area dependence for forward and reverse leakage current density was observed, suggesting that the mesa sidewall provided a leakage path.

42 ENGINEERING↗
DOE OSTI2014

Structural characterization of ion-vapor deposited hydrogenated amorphous carbon coatings by solid state {sup 13}C nuclear magnetic resonance

In the present study, unique structural heterogeneity was observed in ion-vapor deposited a-C:H coatings by performing {sup 13}C MAS and {sup 1}H-{sup 13}C CPMAS experiments on solid state nuclear magnetic resonance devices. Two distinct types of sp{sup 2} C clusters were discovered: one of them denoted as sp{sup 2} C′ in content of 3–12 at. % was non-protonated specifically localized in hydrogen-absent regions, while the other dominant one denoted as sp{sup 2} C″ was hydrogenated or at least proximate to proton spins. On basis of the notably analogous variation of sp{sup 2} C′ content and Raman parameters as function of substrate bias voltage in the whole range of 0.5 kV–3.5 kV, a model of nano-clustering configuration was proposed that the sp{sup 2} C′ clusters were embedded between sp{sup 2} C″ clusters and amorphous sp{sup 3} C matrix as trapped interfaces or boundaries where the sp{sup 2} carbon bonds were highly distorted. Continuous increase of bias voltage would promote the nano-clustering and re-ordering of dominant sp{sup 2} C″ clusters, thus results in a marked decrease of interspace and a change of the content of sp{sup 2} C′ clusters. Further investigation on the {sup 13}C magnetization recovery showed typical stretched-exponential approximation due to the prominent presence of paramagnetic centers, and the stretched power α varied within 0.6–0.9 from distinct types of sp{sup 2} C clusters. Differently, the magnetization recovery of {sup 1}H showed better bi-exponential approximation with long and short T{sub 1}(H) fluctuated within 40–60 ms and 0.1–0.3 ms approximately in content of 80% ± 5% and 20% ± 5%, respectively, varying with various bias voltages. Meanwhile, the interrupted {sup 13}C saturation recovery with an interval of short T{sub 1}(H) showed that most of quick-relaxing protons were localized in sp{sup 2} C″ clusters. Such a short T{sub 1}(H) was only possibly resulted from a relaxation mechanism associated with electron-nuclear dipolar interaction or spinning diffusion, and its partial distribution in sp{sup 2} C″ clusters may imply more complex configurations of unpaired electrons in studied a-C:H coatings.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Room-temperature single-photon emitters in silicon nitride

Single-photon emitters are essential in enabling several emerging applications in quantum information technology, quantum sensing, and quantum communication. Scalable photonic platforms capable of hosting intrinsic or embedded sources of single-photon emission are of particular interest for the realization of integrated quantum photonic circuits. Here, we report on the observation of room-temperature single-photon emitters in silicon nitride (SiN) films grown on silicon dioxide substrates. Photophysical analysis reveals bright (>10 5 counts/s), stable, linearly polarized, and pure quantum emitters in SiN films with a second-order autocorrelation function value at zero time delay g (2) (0) below 0.2 at room temperature. We suggest that the emission originates from a specific defect center in SiN because of the narrow wavelength distribution of the observed luminescence peak. Single-photon emitters in SiN have the potential to enable direct, scalable, and low-loss integration of quantum light sources with a well-established photonic on-chip platform.

42 ENGINEERING↗
DOE OSTI2013

Development of Pollution Prevention Technologies

This project investigated technologies that may reduce environmental pollution. This was a basic research/educational project addressing two major areas: A. In the algae research project, newly isolated strains of microalgae were investigated for feedstock production to address the production of renewable fuels. An existing collection of microalgae was screened for lipid composition to determine strains with superior composition of biofuel molecules. As many microalgae store triacylglycerides in so-called oil bodies, selected candidate strains identified from the first screen that accumulate oil bodies were selected for further biochemical analysis, because almost nothing was known about the biochemistry of these oil bodies. Understanding sequestration of triacylglycerides in intracellular storage compartments is essential to developing better strains for achieving high oil productivities by microalgae. At the onset of the project there was almost no information available on how to obtain detailed profiles of lipids from strains of microalgae. Our research developed analytical methods to determine the lipid profiles of novel microalgal strains. The project was embedded into other ongoing microalgal projects in the Polle laboratory. The project benefited the public, because students were trained in cell cultivation and in the operation of state-of-the-art analytical equipment. In addition, students at Brooklyn College were introduced into the concept of a systems biology approach to study algal biofuels production. B. A series of new nanostructured catalysts were synthesized, and characterized by a variety of physical and chemical methods. Our catalyst design leads to active nanostructures comprising small metal particles in intimate contact with strongly basic sites provided by the supports, which include poly(4-vinylpyridine), magnesium oxide, functionalized multi-walled carbon nanotubes, and graphene oxide. The new materials display a good potential as catalysts for reactions of relevance to the manufacture of cleaner fossil fuels and biodiesel, and to hydrogen storage in organic liquids. Specifically the catalysts are highly active in the hydrogenation of aromatic and heteroaromatic components of fossil fuels, the reduction of unsaturated C=C bonds in biodiesel, and the dehydrogenation of nitrogen heterocycles. In the course of our studies we identified a novel dual-site substrate-dependent hydrogenation mechanism that explains the activity and selectivity data obtained and the resistance of the new catalysts to poisoning. These results represent an important advance in basic catalytic science, regarding design and synthesis and reaction mechanisms. Additionally, this project allowed the enhancement of the laboratory facilities in the Chemistry Department of Brooklyn College for catalysis and energy research, and served as an excellent vehicle for the training of several young researchers at the undergraduate, graduate and postdoctoral level, to join the national scientific workforce.

09 BIOMASS FUELS↗
NASA NTRS1985

Oxidation resistant slurry coating for carbon-based materials

An oxidation resistant coating is produced on carbon-base materials, and the same processing step effects an infiltration of the substrate with silicon containing material. The process comprises making a slurry of nickel and silicon powders in a nitrocellulose lacquer, spraying onto the graphite or carbon-carbon substrate, and sintering in vacuum to form a fused coating that wets and covers the surface as well as penetrates into the pores of the substrate. Optimum wetting and infiltration occurs in the range of Ni-60 w/o Si to Ni-90 w/o Si with deposited thicknesses of 25-100 mg/sq. cm. Sintering temperatures of about 1200 C to about 1400 C are used, depending on the melting point of the specific coating composition. The sintered coating results in Ni-Si intermetallic phases and SiC, both of which are highly oxidation resistant.

Smialek, J. L.↗
NASA NTRS1997

Development of Sintered Fiber Nickel Electrodes for Aerospace Batteries

The nickel electrode is the specific energy limiting component in nickel battery systems. A concerted effort is currently underway to improve NiH2 performance while decreasing system cost. Increased performance with electrode specific energy (mAh/g) is the major goal of this effort. However, cost reduction is also an important part of the overall program, achieved by reducing the electrode weight. A lightweight, high energy density, nickel electrode is being, developed based on a highly porous, sintered fiber, nickel substrate. This developing technology has many applications, but is highly, applicable to the military and aerospace industries.

Francisco, Jennifer↗
DOE OSTI2024

Copper and bismuth-based sorbent characterization in simulated iodine off-gas streams

The effective capture of volatile radioiodine, a fission product present in used nuclear fuel (UNF), is of paramount importance for development of used fuel reprocessing schemes to prevent release of radioiodine during unit operations and to meet regulatory standards for air emissions. A well-studied method for iodine capture in off-gas streams is the use of silver-functionalized zeolite phases (AgZ), which exploit chemisorption of I to Ag. Advances into other Ag-functionalized materials, including aerogels and metal organic frameworks (MOFs), are underway [1]. Additional metals with the capability to chemisorb iodine, including Cu, Bi, and Sn, [1] are being evaluated as alternatives to Ag for potential applicability to iodine management in off-gas systems. The design of novel functionalized sorbents with Cu and Bi, including composites with metal particles embedded in PAN substrates [2] and composites with metal sulfides embedded in PAN [3], is an ongoing area of study for improved iodine capture. Previously reported work on novel PAN-based metal sorbents has provided the synthesis, characterization, and iodine capture efficiency of this new class of sorbent. Specifically, the metal sulfide PAN composites are found to be easy to produce and reproduce, as well as having a high iodine loading potential under static conditions [3]. Due to the favorable testing previously performed with metal sulfide PAN composites, further testing into the performance of these composites under gas streams containing I2(g) in combination with NO2(g) and H2O(g) is needed. Humid streams of NO2(g) may arise from dissolver off-gas streams, when used fuel is dissolved in HNO3(aq) [4]. NO2(g) has been found to reduce AgZ sorption capacity for I because of oxidation of Ag, the chemisorbing agent, to Ag2O [5]. It follows that performance evaluation of novel sorbents under highly oxidizing conditions such as NO2(g) streams is critical. Therefore, the objective of this study is to determine the effect of flowing NO2(g) and H2O(g) streams on iodine sorption capacity and sorbent performance. This work utilizes custom-built gas handling capabilities for sorbent exposure along with solid-state characterization techniques to assess the physical and chemical properties of sorbents before and after exposure.

copper, bismuth, iodine capture, iodine sorbent, p↗
DOE OSTI2018

Freestanding RGO—Co 3 O 4 —PPy Composite Films as Electrodes for Supercapacitors

Supercapacitors are of great importance for energy storage and have been the subject of intensive research in recent years, in which conductive polymers are used to make flexible and freestanding electrodes. However, their insufficient access to the electrolytes and the low chemical stability of these conductive polymers lead to their poor performance. To solve these issues, a facile method that can be used to synthesize freestanding composite film electrodes of reduced graphene oxide–cobalt oxide–polypyrrole (RGO—Co 3 O 4 —PPy) as supercapacitors is demonstrated. They exhibit a high specific capacitance of 532.8 F g -1 and nearly no degradation after 700 cycles of charging and discharging. The synergistic effect of Co 3 O 4 , RGO, and PPy is responsible for the superior property. The three-phase composite electrode utilizes the RGO nanosheet as a substrate to provide a large surface area for loading Co 3 O 4 nanoparticles and also to enhance the electron transfer. Further, the deposition of PPy largely reduces the resistivity of RGO—Co 3 O 4 —PPy, and the introduction of Co 3 O 4 nanoparticles significantly improves cycle stability.

25 ENERGY STORAGE↗
DOE OSTI2018

Revealing the beneficial role of K in grain interiors, grain boundaries, and at the buffer interface for highly efficient CuInSe 2 solar cells

K incorporation within grain boundaries, grain interiors, and interfaces has been studied within CuInSe 2 solar cells to better understand the beneficial or detrimental role of K distribution among these regions in chalcopyrite–based solar cells. Solar cells have been fabricated with intentional K introduction into specific regions of the device including the CuInSe 2 /CdS interface (CuInSe 2 /KInSe 2 /CdS) and the grain interiors (Cu 0.93 K 0.07 InSe 2 /CdS). A control CuInSe 2 /CdS device was also studied to separate effects of K originating from the soda–lime glass substrate from those of intentionally introduced K. The experiment was designed to understand K effects in Cu(In,Ga)Se 2 solar cells while mitigating complications from multiple elements in the 3 + site. The distribution of all elements within these samples has been directly observed with sub–nm resolution via atom probe tomography. In addition, electron beam–induced current measurements have been performed to correlate the atom probe tomography compositional profiles to the nanoscale carrier collection properties. The experiments show that a large decrease in the Cu/In ratio at the CdS interface can be achieved by forming KInSe 2 at the absorber surface, which drastically improves the device efficiency. The results presented here show a direct link between K concentration, Cu depletion, and In accumulation, such that the Cu/In ratio significantly reduces with K incorporation. In conclusion, the findings help clarify the mechanism behind K–induced efficiency enhancement.

14 SOLAR ENERGY↗
DOE OSTI2015

Pronounced Size Dependence in Structure and Morphology of Gas-Phase Produced, Partially Oxidized Cobalt Nanoparticles under Catalytic Reaction Conditions

It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 nm and 22nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.

cluster source↗
DOE OSTI2014

Predicting the influence of long-range molecular interactions on macroscopic-scale diffusion by homogenization of the Smoluchowski equation

The macroscopic diffusion constant for a charged diffuser is in part dependent on (1) the volume excluded by solute “obstacles” and (2) long-range interactions between those obstacles and the diffuser. Increasing excluded volume reduces transport of the diffuser, while long-range interactions can either increase or decrease diffusivity, depending on the nature of the potential. We previously demonstrated [P. M. Kekenes-Huskey et al., Biophys. J. 105, 2130 (2013)] using homogenization theory that the configuration of molecular-scale obstacles can both hinder diffusion and induce diffusional anisotropy for small ions. As the density of molecular obstacles increases, van der Waals (vdW) and electrostatic interactions between obstacle and a diffuser become significant and can strongly influence the latter's diffusivity, which was neglected in our original model. Here, we extend this methodology to include a fixed (time-independent) potential of mean force, through homogenization of the Smoluchowski equation. We consider the diffusion of ions in crowded, hydrophilic environments at physiological ionic strengths and find that electrostatic and vdW interactions can enhance or depress effective diffusion rates for attractive or repulsive forces, respectively. Additionally, we show that the observed diffusion rate may be reduced independent of non-specific electrostatic and vdW interactions by treating obstacles that exhibit specific binding interactions as “buffers” that absorb free diffusers. Finally, we demonstrate that effective diffusion rates are sensitive to distribution of surface charge on a globular protein, Troponin C, suggesting that the use of molecular structures with atomistic-scale resolution can account for electrostatic influences on substrate transport. This approach offers new insight into the influence of molecular-scale, long-range interactions on transport of charged species, particularly for diffusion-influenced signaling events occurring in crowded cellular environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗