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DOE OSTI2024

Methyl Termination of p-Type Silicon Enables Selective Photoelectrochemical CO 2 Reduction by a Molecular Ruthenium Catalyst

Methyl-terminated p-type silicon photoelectrodes selectively drive CO 2 reduction by a homogeneous [Ru(tpy)(Mebim-py)(NCCH 3 )] 2+ catalyst (tpy = 2,2′:6′,2″-terpyridine, Mebim-py = 1-methylbenzimidazol-2-ylidene-3-(2′-pyridine)). A 460 mV photovoltage is quantified for the photoelectrode. Under 1 sun illumination, this system achieves a Faradaic efficiency of 87% for CO at −1.7 V vs Fc +/0 , matching reports of the same catalyst at metallic electrodes operating at −2.1 V. When 5% water is introduced, the CH 3 -terminated Si photoelectrode remains stable, selectivity for CO is retained, and current density increases. Methyl termination suppresses the competitive hydrogen evolution observed for H-terminated Si photoelectrodes, which under the same conditions produce ca. 60% CO and 8% H 2 and have unstable performance. Furthermore, these results establish that a semiconductor photoelectrode can power a molecular CO 2 reduction catalyst without hydrogen evolution by the photoelectrode itself. Methyl termination of p-Si allows CO 2 reduction to kinetically outcompete proton reduction, revealing an important design principle for selective fuel formation.

Catalysts↗

DOE OSTI2024

Single-Shot Readout and Weak Measurement of a Tin-Vacancy Qubit in Diamond

The negatively charged tin-vacancy center in diamond (SnV − ) is an emerging platform for building the next generation of long-distance quantum networks. This is due to the SnV − ’s favorable optical and spin properties including bright emission, insensitivity to electronic noise, and long spin coherence times at temperatures above 1 K. Here, we demonstrate measurement of a single SnV − electronic spin with a single-shot readout fidelity of 87.4%, which can be further improved to 98.5% by conditioning on multiple readouts. In the process, we develop understanding of the relationship between strain, magnetic field, spin readout, and microwave spin control. We show that high-fidelity readout is compatible with rapid microwave spin control, demonstrating a favorable parameter regime for use of the SnV − center as a high-quality spin-photon interface. Finally, we use weak quantum measurement to study measurement-induced dephasing; this illuminates the fundamental interplay between measurement and decoherence in quantum mechanics, and provides a universal method to characterize the efficiency of color-center spin readout. Taken together, these results overcome an important hurdle in the development of the SnV − -based quantum technologies and, in the process, develop techniques and understanding broadly applicable to the study of solid-state quantum emitters.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

NASA NTRS1993

Measurements and computational analysis of heat transfer and flow in a simulated turbine blade internal cooling passage

Visual and quantitative information was obtained on heat transfer and flow in a branched-duct test section that had several significant features of an internal cooling passage of a turbine blade. The objective of this study was to generate a set of experimental data that could be used to validate computer codes for internal cooling systems. Surface heat transfer coefficients and entrance flow conditions were measured at entrance Reynolds numbers of 45,000, 335,000, and 726,000. The heat transfer data were obtained using an Inconel heater sheet attached to the surface and coated with liquid crystals. Visual and quantitative flow field results using particle image velocimetry were also obtained for a plane at mid channel height for a Reynolds number of 45,000. The flow was seeded with polystyrene particles and illuminated by a laser light sheet. Computational results were determined for the same configurations and at matching Reynolds numbers; these surface heat transfer coefficients and flow velocities were computed with a commercially available code. The experimental and computational results were compared. Although some general trends did agree, there were inconsistencies in the temperature patterns as well as in the numerical results. These inconsistencies strongly suggest the need for further computational studies on complicated geometries such as the one studied.

Russell, Louis M.↗

NASA NTRS1993

Measurements and computational analysis of heat transfer and flow in a simulated turbine blade internal cooling passage

Russell, Louis M.↗

NASA NTRS2004

Imaging Spectrophotometry of the Jet/ISM Interaction in IC5063

IC5063 is a somewhat dusty z=0.0110 S0 galaxy with a Seyfert 2 nucleus. It has a triple radio source that spans 3 arcsec, mostly blueshifted H I absorption that spans 700 km/s, and ionization cones that extend for more than 2 arcmins. We obtained fully sampled [O III]\lambda5007 grids at 0."9 and 70 km/s FWHM resolution using the Rutgers Fabry-Perot system on the Blanco 4m telescope. Complementary long-slit spectra using the RC spectrograph on the Blanco, and Taurus Tunable Filter spectral images in H\alpha and [N II]\lambda6583, were also obtained to assess gaseous ionization conditions. We present the results of our analysis, and correlate spectral structures to those visible in archival WFPC2 images. We find that, in the region near the radio triple, gaseous ionization and line velocity width is tightly correlated, in excellent quantitative agreement with the high-velocity shock regime in the diagnostic emission-line ratio diagrams of Dopita & Sutherland. We separate kinematically gas in normal disk rotation that is illuminated by the AGN in the ionization cones from that agitated mechanically by the jet, and assess the energy input from both processes.

Cecil, G.↗

NASA NTRS1977

Investigation of a CTS solar cell test patch under simulated geomagnetic substorm charging conditions

The CTS solar array technology experiment which consists of a solar cell test patch on the Kapton-substrate solar array and the appertaining electronics unit has been operating in geostationary orbit for nearly 1 year without any malfunction although it is expected to be strongly influenced by charging effects on the array surface. The results of a post-launch test program show that the experiment would not survive a discharge due to electrostatic charging in the test patch area. In a simulated substorm, environment discharges were obtained only below a temperature threshold of about 30 C. With solar illumination, this threshold is reduced below 0 C.

Bogus, K. P.↗

NASA NTRS1992

Development of a machine vision system for automated structural assembly

Research is being conducted at the LaRC to develop a telerobotic assembly system designed to construct large space truss structures. This research program was initiated within the past several years, and a ground-based test-bed was developed to evaluate and expand the state of the art. Test-bed operations currently use predetermined ('taught') points for truss structural assembly. Total dependence on the use of taught points for joint receptacle capture and strut installation is neither robust nor reliable enough for space operations. Therefore, a machine vision sensor guidance system is being developed to locate and guide the robot to a passive target mounted on the truss joint receptacle. The vision system hardware includes a miniature video camera, passive targets mounted on the joint receptacles, target illumination hardware, and an image processing system. Discrimination of the target from background clutter is accomplished through standard digital processing techniques. Once the target is identified, a pose estimation algorithm is invoked to determine the location, in three-dimensional space, of the target relative to the robots end-effector. Preliminary test results of the vision system in the Automated Structural Assembly Laboratory with a range of lighting and background conditions indicate that it is fully capable of successfully identifying joint receptacle targets throughout the required operational range. Controlled optical bench test results indicate that the system can also provide the pose estimation accuracy to define the target position.

Sydow, P. Daniel↗

DOE OSTI2020

The Prevalence of Anions at Plasmonic Nanojunctions: A Closer Look at P-Nitrothiophenol

We revisit the reductive coupling of p-nitrothiophenol (NTP) to form dimercaptoazobenzene (DMAB), herein monitored through gap-mode tip-enhanced Raman spectroscopy (TERS) and nano-imaging. We employ a plasmonic Au probe (100 nm diameter at its apex) illuminated with a 633 nm laser source (50 ?W/?m2 at the sample position) to image a NTP-coated faceted silver nanoparticle (~70 nm diameter). A detailed analysis of the recorded spectra reveals that anionic NTP species contribute to the recorded spectral images, in addition to the more thoroughly described DMAB product. Notably, the signatures of the anions are more pronounced than those of the DMAB product under our present experimental conditions. Our results thus demonstrate that anions and their spectral signatures must be considered in the analysis of plasmon-enhanced spectra and images.

Wang, Chih-Feng↗

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↗

NASA NTRS1982

Low-background performance of a monolithic InSb CCD array

A 20 element monolithic InSb charge coupled device (CCD) detector array was measured under low background conditions to assess its potential for orbital astronomical applications. At a temperature of 64 K, previous results for charge transfer efficiency (CTE) were reproduced, and a sensitivity of about 2 x 10 to the minus 15th power joules was measured. At 27 and 6 K, extended integration times were achieved, but CTE was substantially degraded. The noise was approximately 6000 charges, which was in excess of the level where statistical fluctuations from the illumination could be detected. A telescope demonstration was performed showing that the array sensitivity and difficulty of operation were not substantially different from laboratory levels. Ways in which the device could be improved for astronomical applications were discussed.

Bregman, J. D.↗

NASA NTRS1977

Outer Space Research Helps Color Habitability in Earth Interiors

Color is one of the most important elements in making an environment habitable. Both color and light level combine to create comfortable and efficient work areas and satisfying leisure time environments. Indeed, without light, color cannot even be experienced. It is vitally important for the designer to understand the subject of habitability and to know how to make a positive impact upon the habitability of spaces through the application of proven principles of color-design developed by the scientific community. Consider some of these possibilities and pitfalls: A color chosen in broad daylight will not appear the same under dim lighting conditions. If a designer were creating a dimly lit cocktail lounge, for example, there is little sense in using dark colors, which also tend to be more expensive. When the eyes have dark-adapted for even five minutes, any color reflecting 20 percent or less will appear black, and the color experience will be lost. Therefore, surface reflectances should be kept at least above 20 to 25 percent to maintain color where illumination is at low levels. In effect, for lower reflectance surfaces, higher levels of illumination are required to produce the most accurate color discriminability.

Haines, Richard F.↗

NASA NTRS1971

The calculation of electromagnetic fields in the Fresnel and Fraunhofer regions using numerical integration methods

Some results obtained with a digital computer program written at Goddard Space Flight Center to obtain electromagnetic fields scattered by perfectly reflecting surfaces are presented. For purposes of illustration a paraboloidal reflector was illuminated at radio frequencies in the simulation for both receiving and transmitting modes of operation. Fields were computed in the Fresnel and Fraunhofer regions. A dual-reflector system (Cassegrain) was also simulated for the transmitting case, and fields were computed in the Fraunhofer region. Appended results include derivations which show that the vector Kirchhoff-Kottler formulation has an equivalent form requiring only incident magnetic fields as a driving function. Satisfaction of the radiation conditions at infinity by the equivalent form is demonstrated by a conversion from Cartesian to spherical vector operators. A subsequent development presents the formulation by which Fresnel or Fraunhofer patterns are obtainable for dual-reflector systems. A discussion of the time-average Poynting vector is also appended.

Schmidt, R. F.↗

NASA NTRS1976

Conductivity effects in high-voltage spacecraft insulating materials

Laboratory measurements were performed to assess the influence of various external parameters on the conductivity properties of several typical and potential spacecraft insulating materials in a simulated space environment. The materials tested include Kapton, Teflon, quartz, and polyvinylidene fluoride. The parameters measured comprise sample thickness, temperature, applied voltage, illumination intensity and wavelength, and electron beam energy and current density. All tests were conducted in a vacuum chamber at a pressure of about one millionth Torr both with conventional optically-transparent gold front-surface electrodes and with the front surfaces of the test samples exposed directly to an electron beam. The data presented illustrate some of the complexities in electrical characteristics exhibited by the materials as a result of interactions with various conditions of their environment.

Adamo, R. C.↗

NASA NTRS1999

Portable flash lamp reflectance analyzer system and method

The system and method allow spectroscopic analysis of vegetation or the like without effects from changing sun and cloud conditions, undesired portions of the area of interest or atmospheric disturbances. The system (1) includes a light source (5) such as a xenon flash lamp, a telescope (7), a spectrometer (9), an analog/digital converter (11), a memory (13), a display (15), and an on-board microprocessor (17) or a port (19) for attachment to a laptop computer. The system is taken to an area of interest in the woods (step 41), the vegetation is illuminated from below (step 43) and data are taken (step 45).

Kalshoven, James Edward↗

NASA NTRS2011

Project Report: Reducing Color Rivalry in Imagery for Conjugated Multiple Bandpass Filter Based Stereo Endoscopy

A pair of conjugated multiple bandpass filters (CMBF) can be used to create spatially separated pupils in a traditional lens and imaging sensor system allowing for the passive capture of stereo video. This method is especially useful for surgical endoscopy where smaller cameras are needed to provide ample room for manipulating tools while also granting improved visualizations of scene depth. The significant issue in this process is that, due to the complimentary nature of the filters, the colors seen through each filter do not match each other, and also differ from colors as seen under a white illumination source. A color correction model was implemented that included optimized filter selection, such that the degree of necessary post-processing correction was minimized, and a chromatic adaptation transformation that attempted to fix the imaged colors tristimulus indices based on the principle of color constancy. Due to fabrication constraints, only dual bandpass filters were feasible. The theoretical average color error after correction between these filters was still above the fusion limit meaning that rivalry conditions are possible during viewing. This error can be minimized further by designing the filters for a subset of colors corresponding to specific working environments.

conjugated multiple bandpass filters (CMBF)↗

NASA NTRS2004

Stomatal conductance of lettuce grown under or exposed to different light qualities

BACKGROUND AND AIMS: The objective of this research was to examine the effects of differences in light spectrum on the stomatal conductance (Gs) and dry matter production of lettuce plants grown under a day/night cycle with different spectra, and also the effects on Gs of short-term exposure to different spectra. METHODS: Lettuce (Lactuca sativa) plants were grown with 6 h dark and 18 h light under four different spectra, red-blue (RB), red-blue-green (RBG), green (GF) and white (CWF), and Gs and plant growth were measured. KEY RESULTS AND CONCLUSIONS: Conductance of plants grown for 23 d under CWF rose rapidly on illumination to a maximum in the middle of the light period, then decreased again before the dark period when it was minimal. However, the maximum was smaller in plants grown under RB, RGB and GF. This demonstrates that spectral quality during growth affects the diurnal pattern of stomatal conductance. Although Gs was smaller in plants grown under RGB than CWF, dry mass accumulation was greater, suggesting that Gs did not limit carbon assimilation under these spectral conditions. Temporarily changing the spectral quality of the plants grown for 23 d under CWF, affected stomatal responses reversibly, confirming studies on epidermal strips. This study provides new information showing that Gs is responsive to spectral quality during growth and, in the short-term, is not directly coupled to dry matter accumulation.

Light↗

NASA NTRS2017

Osteogenic Transcription Regulated by Exaggerated Stretch Loading via Convergent Wnt Signaling

Cell and animal studies conducted onboard the International Space Station and formerly the Shuttle flights have provided data illuminating the deleterious biological response of bone to mechanical unloading. Down regulation of proliferative mechanisms within stem cell populations of the osteogenic niche is a suggested mechanism for loss of bone mass. However the intercellular communicative cues from osteoblasts and osteocytes in managing stem cell proliferation and osteogenic differentiation are largely unknown. In this investigation, MLO-Y4 osteocyte-like and MC3T3-E1 osteoblast-like cells, are co-culture under dynamic tensile conditions and evaluated for phenotypic expression of biochemical signaling proteins influential in driving stem cell differentiation. MLO-Y4 and MC3T3-E1 were co-cultured on polyethersulfone membrane with a 0.45m porosity to permit soluble factor transfer and direct cell-cell gap junction signaling. Cyclic tensile stimulation was applied for 48 h at a frequency of 0.1Hz and strain of 0.1. Total Live cell counts indicate mechanical activation of MC3T3-E1s inhibits proliferation while MLO-Y4s increase in number. However, the percent of live MLO-Y4s within the population is low (46.3 total count, *p0.05, n4) suggesting a potential apoptotic signaling cascade. Immunofluorescence demonstrated that stimulation of co-cultures elicits increased gap junction communication. Previously reported PCR evaluation of osteogenic markers further corroborate that the co-cultured populations communicative networks play a role in translating mechanical signals to molecular messaging. These findings suggest that an osteocyte-osteoblast signaling feedback mechanism may regulate mechanotransduction of an apoptotic cascade within osteocytes and transcription of cytokine signaling proteins responsible for stem cell niche recruitment much more directly than previously believed.

mechanical stimulation↗

DOE OSTI2026

Catalytic resonance theory for the kinetics of photon-promoted catalysis

The illumination of catalytic surfaces with a continuous or pulsed stream of photons dynamically modulates surface chemistry for faster rates, non-equilibrium conversion, or product selectivity control. To establish fundamental principles of dynamic photon-modulated catalysis, the photocatalytic conversion of a generic surface reaction was simulated using the kinetic Monte Carlo method to understand the kinetic implications of an independent stream of photons that promotes surface product desorption. The time-averaged photocatalytic rate at differential conditions for varying photon flux and temperatures indicated three kinetic regimes described by product thermal desorption control, surface reaction control, and an intermediate kinetic regime with a zero slope Arrhenius plot, consistent with a degree of rate control dominated by the photon arrival frequency (i.e., per-site photon flux). Here, the maximum photocatalytic rate occurred orders of magnitude above the Sabatier limit at the resonance frequency, identified as the photon arrival frequency matching the surface reaction rate constant.

Canavan, Jesse R. [University of Minnesota, Minnea↗