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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Airloads and Wake Geometry Calculations for an Isolated Tiltrotor Model in a Wind Tunnel

Th tiltrotor aircraft configuration has the potential to revolutionize air transportation by providing an economical combination of vertical take-off and landing capability with efficient, high-speed cruise flight. To achieve this potential it is necessary to have validated analytical tools that will support future tiltrotor aircraft development. These analytical tools must calculate tiltrotor aeromechanical behavior, including performance, structural loads, vibration, and aeroelastic stability, with an accuracy established by correlation with measured tiltrotor data. For many years such correlation has been performed for helicopter rotors (rotors designed for edgewise flight), but correlation activities for tiltrotors have been limited, in part by the absence of appropriate measured data. The recent test of the Tilt Rotor Aeroacoustic Model (TRAM) with a single, U4-scale V-22 rotor in the German-Dutch Wind Tunnel (DNW) now provides an extensive set of aeroacoustic, performance, and structural loads data. This paper will present calculations of airloads, wake geometry, and performance, including correlation with TRAM DNW measurements. The calculations were obtained using CAMRAD II, which is a modern rotorcraft comprehensive analysis, with advanced models intended for application to tiltrotor aircraft as well as helicopters. Comprehensive analyses have received extensive correlation with performance and loads measurements on helicopter rotors. The proposed paper is part of an initial effort to perform an equally extensive correlation with tiltrotor data. The correlation will establish the level of predictive capability achievable with current technology; identify the limitations of the current aerodynamic, wake, and structural models of tiltrotors; and lead to recommendations for research to extend tiltrotor aeromechanics analysis capability. The purpose of the Tilt Rotor Aeroacoustic Model (TRAM) experimental project is to provide data necessary to validate tiltrotor performance and aeroacoustic prediction methodologies and to investigate and demonstrate advanced civil tiltrotor technologies. The TRAM project is a key part of the NASA Short Haul Civil Tiltrotor (SHCT) project. The SHCT project is an element of the Aviation Systems Capacity Initiative within NASA. In April-May 1998 the TRAM was tested in the isolated rotor configuration at the Large Low-speed Facility of the German-Dutch Wind Tunnels (DNW). A preparatory test was conducted in December 1997. These tests were the first comprehensive aeroacoustic test for a tiltrotor, including not only noise and performance data, but airload and wake measurements as well. The TRAM can also be tested in a fill-span configuration, incorporating both rotors Lnd a fuselage model. The wind tunnel installation of the TRAM isolated rotor is shown. The rotor tested in the DNW was a 1/4-scale (9.5 ft diameter) model of the right-hand V-22 proprotor. The rotor and nacelle assembly was attached to an acoustically-treated, isolated rotor test stand through a mechanical pivot (the nacelle conversion axis). The TRAM was analyzed using the rotorcraft comprehensive analysis CAMRAD II. CAMRAD II is an aeromechanical analysis of helicopters and rotorcraft that incorporates a combination of advanced technologies, including multibody dynamics, nonlinear finite elements, and rotorcraft aerodynamics. The trim task finds the equilibrium solution (constant or periodic) for a steady state operating condition, in this case a rotor operating in a wind tunnel. For wind tunnel operation, the thrust and flapping are trimmed to target values. The aerodynamic model includes a wake analysis to calculate the rotor nonuniform induced-velocities, using a free wake geometry. The paper will present the results of CAMRAD II calculations compared to the TRAM DNW measurements for hover performance, helicopter mode performance, and helicopter mode airloads. An example of the hover performance results, comparing both mearements and calculations for the JVX (large scale) and TRAM (small scale) rotors, is shown. An example of the helicopter mode performance, showing the influence of the aerodynamic model (particularly the stall delay model) on the calculated power, induced power, and profile power is also shown. An example of the helicopter mode airloads, showing the influence of various wake and aerodynamic models on the calculations, is shown. Good correlation with measured airloads is obtained using the multiple-trailer wake model. The paper will present additional results, and describe and discuss the aerodynamic behavior in detail.

Johnson, Wayne↗
DOE OSTI2025

Microwave-Assisted Activation of Mo/HZSM5 in Methane Dehydroaromatization

Natural gas flaring is a significant challenge for oil and gas producers. One viable option to mitigate flaring is the conversion of natural gas into valuable chemicals. Applying microwave energy to heterogenous catalyst materials offers advantages in terms of higher rates and product selectivities in comparison to traditional thermal systems which can be designed for on-demand chemical production in modular reactor systems. Methane dehydroaromatization (MDHA) produces transportable, liquid aromatic products directly from natural gas, which is ideal for remote production but is hindered by low thermodynamic yields and rapid deactivation. The stability and performance of the Mo/ZSM5 catalyst is often determined by the state and nature of Mo in the catalyst, which in turn is dictated by the temperature and gaseous environment during catalyst activation. In this study, the Mo/HZSM5 catalyst was activated under three different heating modes (thermal, microwave E-field, and microwave H-field) and four different gas environments (CO, He, CH4+H2, and H2). All the activated catalysts were characterized using different tools and performance evaluated in MDHA.

methane dehydroaromatization↗
NASA NTRS2014

A Highly Sensitive Multi-Element HgCdTe E-APD Detector for IPDA Lidar Applications

An HgCdTe electron avalanche photodiode (e-APD) detector has been developed for lidar receivers, one application of which is integrated path differential absorption lidar measurements of such atmospheric trace gases as CO2 and CH4. The HgCdTe APD has a wide, visible to mid-wave-infrared, spectral response, high dynamic range, substantially improved sensitivity, and an expected improvement in operational lifetime. A demonstration sensor-chip assembly consisting of a 4.3 lm cutoff HgCdTe 4 9 4 APD detector array with 80 micrometer pitch pixels and a custom complementary metal-oxide-semiconductor readout integrated circuit was developed. For one typical array the APD gain was 654 at 12 V with corresponding gain normalized dark currents ranging from 1.2 fA to 3.2 fA. The 4 9 4 detector system was characterized at 77 K with a 1.55 micrometer wavelength, 1 microsecond wide, laser pulse. The measured unit gain detector photon conversion efficiency was 91.1%. At 11 V bias the mean measured APD gain at 77 K was 307.8 with sigma/mean uniformity of 1.23%. The average, noise-bandwidth normalized, system noise-equivalent power (NEP) was 1.04 fW/Hz(exp 1/2) with a sigma/mean of 3.8%. The measured, electronics-limited, bandwidth of 6.8 MHz was more than adequate for 1 microsecond pulse detection. The system had an NEP (3 MHz) of 0.4 fW/Hz(exp 1/2) at 12 V APD bias and a linear dynamic range close to 1000. A gain-independent quantum-limited SNR of 80% of full theoretical was indicative of a gain-independent excess noise factor very close to 1.0 and the expected APD mode quantum efficiency.

NEP↗
NASA NTRS2014

High-Precision Measurement of Eu/Eu* in Geological Glasses via LA-ICP-MS Analysis

Elemental fractionation during laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis has been historically documented between refractory and volatile elements. In this work, however, we observed fractionation between light rare earth elements (LREEs) and heavy rare earth elements (HREEs) when using ablation strategies involving large spot sizes (greater than 100 millimeters) and line scanning mode. In addition: (1) ion yields decrease when using spot sizes above 100 millimeters; (2) (Eu/Eu*)(sub raw) (i.e. Europium anomaly) positively correlates with carrier gas (He) flow rate, which provides control over the particle size distribution of the aerosol reaching the ICP; (3) (Eu/Eu*)(sub raw) shows a positive correlation with spot size, and (4) the changes in REE signal intensity, induced by the He flow rate change, roughly correlate with REE condensation temperatures. The REE fractionation is likely driven by the slight but significant difference in their condensation temperatures. Large particles may not be completely dissociated in the ICP and result in preferential evaporation of the less refractory LREEs and thus non-stoichiometric particle-ion conversion. This mechanism may also be responsible for Sm-Eu-Gd fractionation as Eu is less refractory than Sm and Gd. The extent of fractionation depends upon the particle size distribution of the aerosol, which in turn is influenced by the laser parameters and matrix. Ablation pits and lines defined by low aspect ratios produce a higher proportion of large particles than high aspect ratio ablation, as confirmed by measurements of particle size distribution in the laser induced aerosol. Therefore, low aspect ratio ablation introduces particles that cannot be decomposed and/or atomized by the ICP and thus results in exacerbated elemental fractionation. Accurate quantification of REE concentrations and Eu/Eu* requires reduction of large particle production during laser ablation. For the reference materials analyzed in this work, the 100 millimeters spot measurements of Eu/Eu* agreed with GeoRem preferred values within 3 percent. Our long-term analyses of Eu/Eu* in MPI-DING glass KL-2G and USGS glass BIR-1G were reproducible at 3 percent (2 RSD).

geological glasses↗
NASA NTRS1979

Isis 1 observations at the source of auroral kilometric radiation

Observations of auroral kilometric radiation (AKR) were made by Isis 1 in the source region. The radiation is found to be generated in the extraordinary mode just above the local cut-off frequency and to emanate nearly perpendicular to the magnetic field. It occurs within local depletions of electron density, where the ratio of plasma frequency to cyclotron frequency is less than 0.2. The density depletion is restricted to altitudes above about 2000 km, and the upper AKR frequency limit corresponds to the extraordinary cut-off frequency at this altitude. AKR is observed from Isis 1 above the nighttime auroral zone over a wider extent in longitude than in latitude with an intense source region observed most often near 2200 LMT and 70 deg invariant latitude. It is directly related to inverted V electron precipitation events with an electron-to-wave energy conversion efficiency of the order of 0.1 to 1%.

Benson, R. F.↗
NASA NTRS1995

Electronic collection system for spacelab mission timeline requirements

This paper describes the Functional Objective Requirements Collection System (FORCS) software tool that has been developed for use by Principal Investigators (PI's) and Payload Element Developers (PED's) on their own personal computers to develop on-orbit timelining requirements for their payloads. The FORCS tool can be used either in a totally stand-alone mode, storing the information in a local file on the user's personal computer hard disk or in a remote mode where the user's computer is linked to a host computer containing the integrated database of the timeline requirements for all of the payloads on a mission. There are a number of features incorporated in the FORCS software to assist the user. The user may move freely back and forth between the various forms for inputting the data. Several methods are used to input the information, depending on the type of the information. These methods range from filling in text boxes, using check boxes and radio buttons, to inputting information into a spreadsheet format. There are automated features provided to assist in developing the proper format for the data, ranging from limit checking on some of the parameters to automatic conversion of different formats of time data inputs to the one standard format used for the timeline scheduling software.

Lindberg, James P.↗
NASA NTRS2008

Single-mode, All-Solid-State Nd:YAG Laser Pumped UV Converter

In this paper, the status of a high-energy, all solid-state Nd:YAG laser pumped nonlinear optics based UV converter development is discussed. The high-energy UV transmitter technology is being developed for ozone sensing applications from space based platforms using differential lidar technique. The goal is to generate greater than 200 mJ/pulse with 10-50 Hz PRF at wavelengths of 308 nm and 320 nm. A diode-pumped, all-solid-state and single longitudinal mode Nd:YAG laser designed to provide conductively cooled operation at 1064 nm has been built and tested. Currently, this pump laser provides an output pulse energy of >1 J/pulse at 50 Hz PRF and a pulsewidth of 22 ns with an electrical-to-optical system efficiency of greater than 7% and a M(sup 2) value of <2. The single frequency UV converter arrangement basically consists of an IR Optical Parametric Oscillator (OPO) and a Sum Frequency Generator (SFG) setups that are pumped by 532 nm wavelength obtained via Second Harmonic Generation (SHG). In this paper, the operation of an inter cavity SFG with CW laser seeding scheme generating 320 nm wavelength is presented. Efforts are underway to improve conversion efficiency of this mJ class UV converter by modifying the spatial beam profile of the pump laser.

Prasad, Narasimha S.↗
NASA NTRS1999

Miniature Heat Transport System for Nanosatellite Technology

The scientific understanding of key physical processes between the Sun and the Earth require simultaneous measurements from many vantage points in space. Nano-satellite technologies will enable a class of constellation missions for the NASA Space Science Sun-Earth Connections. This recent emphasis on the implementation of smaller satellites leads to a requirement for development of smaller subsystems in several areas. Key technologies under development include: advanced miniaturized chemical propulsion; miniaturized sensors; highly integrated, compact electronics; autonomous onboard and ground operations; miniatures low power tracking techniques for orbit determination; onboard RF communications capable of transmitting data to the ground from far distances; lightweight efficient solar array panels; lightweight, high output battery cells; lightweight yet strong composite materials for the nano-spacecraft and deployer-ship structures. These newer smaller systems may have higher power densities and higher thermal transport requirements than seen on previous small satellites. Furthermore, the small satellites may also have a requirement to maintain thermal control through extended earth shadows, possibly up to 8 hours long. Older thermal control technology, such as heaters, thermostats, and heat pipes, may not be sufficient to meet the requirements of these new systems. Conversely, a miniature two-phase heat transport system (Mini-HTS) such as a Capillary Pumped Loop (CPL) or Loop Heat Pipe (LBP) is a viable alternative. A Mini-HTS can provide fine temperature control, thermal diode action, and a highly efficient means of heat transfer. The Mini-HTS would have power capabilities in the range of tens of watts or less and provide thermal control over typical spacecraft ranges. The Mini-HTS would allow the internal portion of the spacecraft to be thermally isolated from the external radiator, thus protecting the internal components from extreme cold temperatures during an eclipse. The Mini-HTS would transport the beat from these components to a radiator during their operational modes, and it would be shutdown during non-operational or eclipse modes. Shutdown of the Mini-HTS would be accomplished with small heaters and has been successfully demonstrated on numerous occasions, both in the lab and on flight experiments. Efforts are now underway to miniaturize two-phase heat transport systems for the Nanosatellite project, with potential application to other small satellite programs. 'ne goal of this project is to design, build, and test miniature heat transport systems (MHTS) that would demonstrate the feasibility of a small Capillary Pumped Loop (CPL) or Loop Heat Pipe (LBP).

Douglas, Donya M,↗
DOE OSTI2026

Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure

Swings in pH can be achieved by electrically polarizing a bipolar membrane (BPM) to drive water dissociation at the BPM junction for electrochemical conversion and separation processes. BPM junction design is critical to tailor performance for specific applications; however, characterization techniques capable of resolving the nanometer scale physical structure of the junction are limited. We present sample preparation, imaging, and analysis workflows that are adaptable to a variety of BPM junction architectures. Atomic force microscopy produces BPM junction images with nanometer scale lateral resolution for samples with and without a graphene oxide water dissociation catalyst in the junction. Subsequent image segmentation and analysis quantify line edge roughness and catalyst layer thickness as descriptors of junction structure. Comparison of pre- and post-electrodialysis junctions suggests electric field-induced alignment of catalyst particles during electrodialysis. This characterization workflow can inform manufacturing protocols, computational modeling, and failure mode analysis for next-generation BPMs.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Host analysis-guided selection and targeted engineering (HASTE) of Lipomyces tetrasporus for the conversion of CO2-derived feedstocks

Efficient and cost-competitive bioproduction calls for utilizing CO2-derived feedstocks, such as products from electro-reduction of CO2 and hydrolysate from lignocellulosic biomass. However, efficiently using all their carbon components, including acetate, glucose, and xylose, remains a challenge. Here, we characterize Lipomyces tetrasporus, a novel, robust yeast strain capable of effectively assimilating these carbon sources. We used an integrated systems biology approach combining ¹³C metabolic flux analysis, dynamic labeling experiments, and RNA sequencing. We conducted the first metabolic flux analysis for glucose, xylose, and acetate catabolism in this species. Dynamic labeling revealed a highly active TCA cycle during acetate metabolism, evidenced by rapid citrate and malate accumulation. The strain demonstrated strong NADH/NADPH production and acetyl-CoA synthase activity. Using insights and gene targets from this analysis, we engineered L. tetrasporus for malate production. The engineered strain produced 7.5 g/L malic acid (0.25 g/g yield) in shake flasks with glucose-acetate media and 28.8 g/L malic acid at a yield of 0.20 g/g in fed-batch mode with corn-stover hydrolysate. Together, these insights and rational strain engineering establish L. tetrasporus as a versatile, Crabtree-negative platform that is an energy-CO2-bioproduction nexus for channeling CO2 carbon into value-added bioproducts.

Xiao, Zhengyang↗
DOE OSTI2025

Durability Optimization of CO 2 Electrolyzers for Syngas Evolution

Recently, there has been an increased interest in mitigating anthropogenic CO 2 emissions through the electrochemical conversion of CO 2 into fuels and fuel feedstocks, including hydrogen gas (H 2 ), carbon monoxide (CO), and mixtures of the two to yield syngas. Commercial applications of these systems require high catalytic selectivity for the desired products, while exhibiting operational lifetimes exceeding thousands of hours. Advancements in this field have produced systems that display high selectivity of the desired products at faradaic efficiencies exceeding 95%. Despite the advancements made in CO 2 electrolysis, system durability remains a standing challenge in the field. CO 2 electrolyzer lifetimes are often limited by carbonate fouling, catalyst degradation, detrimental flooding of electrode microporous layers and anion exchange membrane (AEM) failures. In this report, a 5 cm 2 membrane electrode assembly (MEA) device is used to investigate potential failure modes and to optimize AEM CO 2 electrolyzer operation. Key findings of this study include the importance of CO 2 flow rate, use of a thin PiperION PTFE-reinforced membrane, optimizing compression to enhance contact under 40 in-lb compression, and the effect of more compressible, commercial iridium oxide anodes on system durability.

Abouremeleh, Mohammed H. [Lawrence Berkeley Nation↗
NASA NTRS1978

Conceptual design study of a Harrier V/STOL research aircraft

MCAIR recently completed a conceptual design study to define modification approaches to, and derive planning prices for the conversion of a two place Harrier to a V/STOL control, display and guidance research aircraft. Control concepts such as rate damping, attitude stabilization, velocity command, and cockpit controllers are to be demonstrated. Display formats will also be investigated, and landing, navigation and guidance systems flight tested. The rear cockpit is modified such that it can be quickly adapted to faithfully simulate the controls, displays and handling qualities of a Type A or Type B V/STOL. The safety pilot always has take command capability. The modifications studied fall into two categories: basic modifications and optional modifications. Technical descriptions of the basic modifications and of the optional modifications are presented. The modification plan and schedule as well as the test plan and schedule are presented. The failure mode and effects analysis, aircraft performance, aircraft weight, and aircraft support are discussed.

Bode, W. E.↗
NASA NTRS2003

Real-Time Attitude Independent Three Axis Magnetometer Calibration

In this paper new real-time approaches for three-axis magnetometer sensor calibration are derived. These approaches rely on a conversion of the magnetometer-body and geomagnetic-reference vectors into an attitude independent observation by using scalar checking. The goal of the full calibration problem involves the determination of the magnetometer bias vector, scale factors and non-orthogonality corrections. Although the actual solution to this full calibration problem involves the minimization of a quartic loss function, the problem can be converted into a quadratic loss function by a centering approximation. This leads to a simple batch linear least squares solution. In this paper we develop alternative real-time algorithms based on both the extended Kalman filter and Unscented filter. With these real-time algorithms, a full magnetometer calibration can now be performed on-orbit during typical spacecraft mission-mode operations. Simulation results indicate that both algorithms provide accurate integer resolution in real time, but the Unscented filter is more robust to large initial condition errors than the extended Kalman filter. The algorithms are also tested using actual data from the Transition Region and Coronal Explorer (TRACE).

Crassidis, John L.↗
DOE OSTI2023

High spatial resolution direct conversion amorphous selenium X-ray detectors with monolithically integrated CMOS readout

Recent progress in the field of micron-scale spatial resolution direct conversion X-ray detectors for high-energy synchrotron light sources serve applications ranging from nondestructive and noninvasive microscopy techniques which provide insight into the structure and morphology of crystals, to medical diagnostic measurement devices. Amorphous selenium ( a -Se) as a wide-bandgap thermally evaporated photoconductor exhibits ultra-low thermal generation rates for dark carriers and has been extensively used in X-ray medical imaging. Being an amorphous material, it can further be deposited over large areas at room temperatures and at substantially lower costs as compared to crystalline semiconductors. Here, to address the demands for a high-energy and high spatial resolution X-ray detector for synchrotron light source applications, we have thermally evaporated a -Se on a Mixed-Mode Pixel Array Detector (MM-PAD) Application Specific Integrated Circuit (ASIC). The ASIC format consists of 128 × 128 square pixels each 150 μm on a side. A 200 μm a -Se layer was directly deposited on the ASIC followed by a metal top electrode. The completed detector assembly was tested with 45 kV Ag and 23 kV Cu X-ray tube sources. The detector fabrication, performances, Modulation Transfer Function (MTF) measurements, and simulations are reported.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Data for Controlling Circuitry Underlies the Growth Optimization of Saccharomyces cerevisiae

Microbial growth emerges from coordinated synthesis of various cellular components from limited resources. In Saccharomyces cerevisiae , cyclic AMP (cAMP)-mediated signaling is shown to orchestrate cellular metabolism; however, it remains unclear quantitatively how the controlling circuit drives resource partition and subsequently shapes biomass growth. Here we combined experiment with mathematical modeling to dissect the signaling-mediated growth optimization of S. cerevisiae . We showed that, through cAMP-mediated control, the organism achieves maximal or nearly maximal steady-state growth during the utilization of multiple tested substrates as well as under perturbations impairing glucose uptake. However, the optimal cAMP concentration varies across cases, suggesting that different modes of resource allocation are adopted for varied conditions. Under settings with nutrient alterations, S. cerevisiae tunes its cAMP level to dynamically reprogram itself to realize rapid adaptation. Moreover, to achieve growth maximization, cells employ additional regulatory systems such as the GCN2-mediated amino acid control. This study establishes a systematic understanding of global resource allocation in S. cerevisiae , providing insights into quantitative yeast physiology as well as metabolic strain engineering for biotechnological applications.

Conversion↗
DOE OSTI2022

X-point and divertor filament dynamics from gas puff imaging on TCV

Abstract A new gas puff imaging diagnostic has been installed on the TCV tokamak, providing two-dimensional insights into scrape-off-layer (SOL) turbulence dynamics above, at and below the magnetic X-point. A detailed study in L-mode, attached, lower single-null discharges shows that statistical properties have little poloidal variations, while vast differences are present in the 2D behaviour of intermittent filaments. Strongly elongated filaments, just above the X-point and in the divertor far-SOL, show a good consistency in shape and dynamics with field-line tracing from filaments at the outboard midplane, highlighting their connection. In the near-SOL of the outer divertor leg, short-lived, high frequency and more circular (diameter ∼15 sound Larmor radii) filaments are observed. These divertor-localised filaments appear born radially at the position of maximum density and display a radially outward motion with velocity ≈400 m s −1 that is comparable to radial velocities of upstream-connected filaments. Conversely, in these discharges ( B → × ∇ B pointing away from the divertor), these divertor filaments’ poloidal velocities differ strongly from those of upstream-connected filaments. The importance of divertor-localised filaments upon radial transport and profile broadening is explored using filament statistics and in situ kinetic profile measurements along the divertor leg. This suggests that these filaments contribute significantly to electron density profile broadening in the divertor.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Experimental and DFT Calculated IR Spectra of Guests in Zeolites: Acyclic Olefins and Host-Guest Interactions

We performed experimental and periodic density functional theory (DFT) IR spectroscopy to investigate the adsorption of acyclic olefins over both acidic and non-acidic zeolites. Two conjugated polyenes, 2,4-dimethyl-1,3-pentadiene (I) and 2,6-dimethyl-2,4,6-octatriene (II) were studied to probe organic intermediates that can form during methanol conversion, and that can lead to deactivating species known collectively as “coke.” We computed vibrational spectra using zeolite-adsorbed and gas-phase models for both neutral and protonated forms of I and II, and compared these DFT results to diffuse reflectance IR Fourier transform (DRIFT) spectra of zeolite-guest systems. Our experimental and computational results are precise enough to pinpoint that the gauche s-cis conformation of species I predominates during adsorption over de-aluminated zeolite beta. Computed zeolite-adsorbed spectra of the protonated species I and II best represent the DRIFT spectra obtained after the adsorption of the olefins on HMOR at 20 ?, with computed bands at 1543 and 1562 cm–1 for molecules I+ and II+, respectively, attributed to the allylic stretching mode, ?(C=C–C+). These computed band frequencies are within 6 cm–1 of experimental data and confirm that the interaction between neutral acyclic olefins and acidic zeolites leads to protonation of the olefin. Comparison of computed spectra of the protonated species in the gas phase to those in the zeolite indicates that the electrostatic interaction between alkenyl and alkadienyl cations and negative zeolite framework does not significantly impact the position of the allylic stretching bands. These results highlight that computed spectroscopy and thermodynamics coupled with experimental spectra can be used for elucidating complex mixtures in zeolites, and certain spectral features of adsorbed olefins can be accurately modeled by gas-phase calculations. ACKNOWLEDGMENTS BM and SMA were supported by the National Science Foundation under Award # CBET-1512442. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support (or partial support) of this research (#589978-ND5, EDH and FCJ). MDB was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Materials Science and Engineering. CJM was supported by the DOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated by Battelle for the U.S. DOE. Computing resources were generously provided through PNNL’s institutional computing (PIC).

Manookian, Babgen↗
DOE OSTI2024

Photoelectrochemical CO 2 Reduction to CO Enabled by a Molecular Catalyst Attached to High-Surface-Area Porous Silicon

A high-surface-area p-type porous Si photocathode containing a covalently immobilized molecular Re catalyst is highly selective for the photoelectrochemical conversion of CO 2 to CO. It gives Faradaic efficiencies of up to 90% for CO at potentials of –1.7 V (versus ferrocenium/ferrocene) under 1 sun illumination in an acetonitrile solution containing phenol. Here, the photovoltage is approximately 300 mV based on comparisons with similar n-type porous Si cathodes in the dark. Using an estimate of the equilibrium potential for CO 2 reduction to CO under optimized reaction conditions, photoelectrolysis was performed at a small overpotential, and the onset of electrocatalysis in cyclic voltammograms occurred at a modest underpotential. The porous Si photoelectrode is more stable and selective for CO production than the photoelectrode generated by attaching the same Re catalyst to a planar Si wafer. Further, facile characterization of the porous Si-based photoelectrodes using transmission mode FTIR spectroscopy leads to highly reproducible catalytic performance.

14 SOLAR ENERGY↗