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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

CsO x Nanostructures on Au(111): Morphology- and Size-dependent Activity for the Water–Gas Shift Reaction

Alkali oxides are typically used as promoters of heterogeneous catalysts for the water–gas shift (WGS; H 2 O + CO → H 2 + CO 2 ) reaction. On Au(111), CsO x exhibits diverse nanostructures at varying coverages, as revealed by scanning tunneling microscopy. Clusters of cesium oxide (Cs 2 O 2 ) nucleate at elbow sites of the Au(111) herringbone when θ Cs is less than 0.1 ML. Subsequently, these clusters transform into two-dimensional (2D) islands (Cs 2 O, Cs 2 O 2 , CsO 2 ) as the cesium coverage increases (θ Cs > 0.1 ML). Both types of CsO x nanostructures enable the WGS process on Au(111). The highest activity was seen for the cesium oxide clusters which facilitated the partial dissociation of water and binding of CO. The CO ads and OH ads groups were not strongly bound and probably reacted to yield a short-lived HOCO intermediate that led to gaseous H 2 and CO 2 . The 2D islands of CsO x also enabled the WGS but their efficiency was reduced due to the formation of cesium hydroxide compounds (limiting mobility of OH groups) and the generation of CO 3 and C species (blocking of active centers). The fact that the performance of the CsO x /Au(111) catalysts changed dramatically with variations in the chemical properties of the CsO x nanostructures indicates that the alkali oxide was an integral part of the active phase, playing a central role in the activation and conversion of the reactants. To attach the label of “promoter” to CsO x is a simplification that does not help in the design and optimization of catalysts for C1 chemistry. In conclusion, to achieve a rational design, one must consider the structural and chemical properties of the alkali oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Low thermal conductivity in Bi 8 CsO 8 SeX 7 (X = Cl, Br) by combining different structural motifs

Understanding the structure–property relationships of materials in order to supress thermal conductivity is crucial for developing efficient thermoelectric generators and thermal barrier coatings. Low thermal conductivity materials can often contain a single dominant phonon scattering mechanism. Here, we highlight how combining different structural features into one material can aid in the design and identification of new materials with low thermal conductivities. We synthesise two new mixed-anion materials, Bi 8 CsO 8 SeX 7 (X = Cl and Br), with low thermal conductivities of 0.27(2) and 0.22(2) W m -1 K -1 respectively, measured along their c-axes at room temperature. The Bi 8 CsO 8 SeX 7 materials possess a combination of bond strength hierarchies, Cs + vacancies, and low frequency Cs + rattling. These different features significantly inhibit phonon transport along different crystallographic directions. Due to sharp bond strength contrast between the van der Waals gaps and [Bi 2 O 2 ] 2+ layers, the Bi 8 CsO 8 SeX 7 materials exhibit thermal conductivities <50% of the theoretical minimum when measured along the stacking direction. Conversely, the thermal conductivity associated with the ab-plane is reduced by Cs + rattling when compared to the structurally and compositionally related BiOCl.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

XMM-Newton Spectroscopy of the X-ray Detected Broad Absorption Line QSO CSO 755

We present the results from XMM-Newton observations of the highly optically polarized broad absorption line quasar (BALQSO) CSO 755. By analyzing its X-ray spectrum with a total of approximately 3000 photons we find that this source has an X-ray continuum of "typical" radio-quiet quasars, with a photon index of Gamma=1.83, and a rather flat (X-ray bright) intrinsic optical-to-X-ray spectral slope of alpha_ox=- 1.51. The source shows evidence for intrinsic absorption, and fitting the spectrum with a neutral-absorption model gives a column density of N_H approximately 1.2x10^22 cm^{-2}; this is among the lowest X-ray columns measured for BALQSOs. We do not detect, with high significance, any other absorption features in the X-ray spectrum. Upper limits we place on the rest-frame equivalent width of a neutral (ionized) Fe K-alpha line, less than =180 eV (less than =120 eV), and on the Compton-reflection component parameter, R less than =0.2, suggest that most of the X-rays from the source are directly observed rather than being scattered or reflected; this is also supported by the relatively flat intrinsic alpha ox we measure. The possibility that most of the X-ray flux is scattered due to the high level of UV-optical polarization is ruled out. Considering data for 46 BALQSOs from the literature, including CSO 755, we have found that the UV-optical continuum polarization level of BALQSOs is not correlated with any of their X-ray properties. A lack of significant short-term and long-term X-ray flux variations in the source may be attributed to a large black-hole mass in CSO 755. We note that another luminous BALQSO, PG 2112+059, has both similar shallow C IV BALs and moderate X-ray absorption.

Brandt, Niel↗
DOE OSTI2020

Materials Data on CSO by Materials Project

CSO crystallizes in the trigonal R3m space group. The structure is one-dimensional and consists of three CSO ribbons oriented in the (0, 0, 1) direction. C4+ is bonded in a distorted linear geometry to one S2- and one O2- atom. The C–S bond length is 1.56 Å. The C–O bond length is 1.18 Å. S2- is bonded in a linear geometry to one C4+ and one O2- atom. The S–O bond length is 3.34 Å. O2- is bonded in a single-bond geometry to one C4+ and one S2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CSO by Materials Project

CSO crystallizes in the triclinic P1 space group. The structure is one-dimensional and consists of one CSO ribbon oriented in the (1, 1, 1) direction. C4+ is bonded in a distorted linear geometry to one S2- and one O2- atom. The C–S bond length is 1.56 Å. The C–O bond length is 1.18 Å. S2- is bonded in a 2-coordinate geometry to one C4+ and one O2- atom. The S–O bond length is 3.22 Å. O2- is bonded in a single-bond geometry to one C4+ and one S2- atom.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Morphology Dependent Reactivity of CsO $x$ Nanostructures on Au(111): Binding and Hydrogenation of CO 2 to HCOOH

Cesium oxide (CsO $x$ ) nanostructures grown on Au(111) behave as active centers for CO 2 binding and hydrogenation reactions. The morphology and reactivity of these CsO $x$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs 2 O 2 ) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs $y$ O; $y$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO 2 . Moreover, the O atoms in the Cs $y$ O structure undergo a rearrangement upon the adsorption of CO 2 which is a reversible phenomenon. Under CO 2 hydrogenation conditions, the small Cs 2 O 2 clusters are hydroxylated, thereby preventing the adsorption of CO 2 . However, the hydroxylation of the higher coverages of Cs $y$ O did not prevent CO 2 adsorption, and the adsorbed CO 2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H 2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO 2 reaction with hydroxylated Cs $y$ O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO 2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.

03 NATURAL GAS↗
NASA NTRS1988

Submillimeter heterodyne receiver for the CSO telescope

This task is to build a cryogenically cooled 620 to 700 GHz astronomical receiver that will be used as a facility instrument at the CalTech Submillimeter Observatory (CSO) on Mauna Kea, Hawaii. The receiver will have applications as a very high resolution spectrometer to investigate spectral lines in planetary and satellite atmospheres, and comets. The receiver will also be used to make continuum measurements of planets, satellites, and asteroids. During FY88, a scale model (200 GHz) SIS mixer radiometer was built and intrgrated into a cryostat designed for use on the CSO telescope. This system will serve as a model to guide the work on the higher frequency mixer. A solid state local oscillator source that covers two bands in the 600 to 700 GHz has been developed under contract JPL and will be delivered before the end of the year. Work has continued on the SIS materials needed for the 620 to 700 GHz mixer. Test hardware has been developed which allow the 1 to 5 curves for SIS material to be easily measured.

Gulkis, S.↗
NASA NTRS1992

Broad absorption-line time variability in the QSO CSO 203

We present spectroscopy of the BALQSO CSO 203 during four epochs over a 17-month time span. These data show three distinct levels in the broad absorption lines (BALs) of Si IV 1397A and C IV 1549A. We also note possible variations in the N V 1240A and Al III 1857A absorption troughs. A broad-band monitoring effort during this period shows that the continuum level remained constant to within 10 percent. We argue that the triggering mechanism for the absorption-line changes is most likely synchronous with the continuum source photons; however, no correlation with the central source has yet been found. The observed variations are consistent with changes in the ionization level in the broad absorption-line region (BALR). We discuss possible mechanisms for these changes and the implications for the structure of the BALR.

Barlow, Thomas A.↗
NASA NTRS1994

(abstract) Neptune: CO and HCN Distributions from Observations at the CSO

We used the Caltech Submillimeter Observatory (CSO ) to make spatially unresolved observations of the 230.538 GHz 2-1 transition of CO and the 265.886 GHz 3-2 transition of HCN at Neptune. All observations used the 10.4 meter antenna with a double sideband SIS junction heterodyne receiver. Spectra were observed with parallel acousto-optic spectrometers simultaneously providing 580 MHz bandwidth at 0.57 MHz resolution and 50 MHz bandwidth at 0.049 MHz resolution. Observed line shapes agree with prior observations by Rosenqvist et al and Marten et al. Analysis of the line shapes and intensities will yield information about the distributions of CO and HCN in the stratosphere of Neptune, and these results will be compared with previous results. The data imply that the mixing ratios of CO and HCN must decrease with altitude somewhere within the pressure range from 1 to 0.001 mbar. HCN data will also address the sharp saturation-induced decrease in the HCN mixing ratio at the lower levels in the stratosphere.

Caltech Submillimeter Observatory SRO CO carbon mo↗
NASA NTRS2009

Submillimeter (Lambda < 1 mm) Continuum Imaging at CSO: A Retrospective

This contribution is submitted on behalf of all students, postdocs, and staff inspired and supported by Tom Phillips to build an instrument and then wait for low precipitable water vapor. Over the 20 plus years of its existence, the Caltech Submillimeter Observatory (CSO) has seen a succession of ever more powerful detectors to measure continuum emission in the shortest submillimeter bands available from Mauna Kea. These instruments have been trained on the nearest solar systems, the most distant galaxies, and objects in between. I show several images collected over the 5 plus year history of the SHARC II camera and anecdotal comparison with past work.

bolometer detectors↗
NASA NTRS1998

Stability and Phase Noise Tests of Two Cryo-Cooled Sapphire Oscillators

A cryocooled Compensated Sapphire Oscillator (CSO), developed for the Cassini Ka-band Radio Science experiment, and operating in the 8K - 10K temperature range was previously demonstrated to show ultra-high stability of sigma(sub y) = 2.5 x 10 (exp -15) for measuring times 200 seconds less than or equal to tau less than or equal to 600 seconds using a hydrogen maser as reference. We present here test results for a second unit which allows CSO short-term stability and phase noise to be measured for the first time. Also included are design details of a new RF receiver and an intercomparison with the first CSO unit. Cryogenic oscillators operating below about 10K offer the highest possible short term stability of any frequency sources. However, their use has so far been restricted to research environments due to the limited operating periods associated with liquid helium consumption. The cryocooled CSO is being built in support of the Cassini Ka-band Radio Science experiment and is designed to operate continuously for periods of a year or more. Performance targets are a stability of 3-4 x 10 (exp -15) (1 second less than or equal to tau less than or equal to 100 seconds) and phase noise of -73dB/Hz @ 1Hz measured at 34 GHz. Installation in 5 stations of NASA's deep space network (DSN) is planned in the years 2000 - 2002. In the previous tests, actual stability of the CSO for measuring times tau less than or equal to 200 seconds could not be directly measured, being masked by short-term fluctuations of the H-maser reference. Excellent short-term performance, however, could be inferred by the success of an application of the CSO as local oscillator (L.O.) to the JPL LITS passive atomic standard, where medium-term stability showed no degradation due to L.O. instabilities at a level of (sigma)y = 3 x 10 (exp -14)/square root of tau. A second CSO has now been constructed, and all cryogenic aspects have been verified, including a resonator turn-over temperature of 7.907 K, and Q of 7.4 x 10 (exp 8). These values compare to a turn-over of 8.821 K and Q of 1.0 x 10 (exp 9) for the first resonator. Operation of this second unit provides a capability to directly verify for the first time the short-term (1 second less than or equal to tau less than or equal to 200 seconds) stability and the phase noise of the CSO units. The RF receiver used in earlier tests was sufficient to meet Cassini requirements for tau greater than or equal to 10 seconds but had short-term stability limited to 2-4 x 10 (exp -14) at tau = 1 second, a value 10 times too high to meet our requirements. A new low-noise receiver has been designed to provide approximately equal to 10-15 performance at 1 second, and one receiver is now operational, demonstrating again short-term CSO performance with H maser-limited stability. Short-term performance was degraded in the old receiver due to insufficient tuning bandwidth in a 100MHZ quartz VCO that was frequency-locked to the cryogenic sapphire resonator. The new receivers are designed for sufficient bandwidth, loop gain and low noise to achieve the required performance.

Dick, G. John↗
DOE OSTI2024

A comparison of compact, presumably young with extended, evolved radio active galactic nuclei

Context.The triggering and evolution of active galactic nuclei (AGNs) and the interaction of the AGN with its host galaxy is an important topic in extragalactic astrophysics. Radio sources with peaked spectra (peaked spectrum sources, PSS) and compact symmetric objects (CSO) are powerful, compact, and presumably young AGNs and therefore particularly suitable to study aspects of the AGN-host connection. Aims.We use a statistical approach to investigate properties of a PSS-CSO sample that are related to host galaxies and could potentially shed light on the link between host galaxies and AGNs. The main goal is to compare the PSS-CSO sample with a matching comparison sample of extended sources (ECS) to see if the two have significant differences. Methods.We analysed composite spectra, diagnostic line diagrams, multi-band spectral energy distributions (MBSEDs), star formation (SF) indicators, morphologies, and cluster environments for a sample of 121 PSSs and CSOs for which spectra are available from the Sloan Digital Sky Survey (SDSS). The statistical results were compared with those of the ECS sample, where we generally considered the two subsamples of quasi-stellar objects (QSOs) and radio galaxies separately. The analysis is based on a large set of archival data in the spectral range from the ultraviolet to mid-infrared. Results.We find significant differences between the PSS-CSO and the ECS sample. In particular, we find that the ECS sample has a higher proportion of passive galaxies with a lower star formation activity. This applies to both sub-samples (QSOs or radio galaxies) as well as to the entire sample. The star formation rates of the PSS-CSO host galaxies with available data are typically in the range ∼0 to 5 ℳ ⊙ yr −1 , and the stellar masses are in the range 3 × 10 11 to 10 12 ℳ ⊙ . Secondly, in agreement with previous results, we find a remarkably high proportion of PSS-CSO host galaxies with merger signatures. The merger fraction of the PSS-CSO sample is 0.61 ± 0.07, which is significantly higher than that of the comparison sample (0.15 ± 0.06). We suggest that this difference can be explained by assuming that the majority of the PSSs and CSOs cannot evolve to extended radio sources and are therefore not represented in our comparison sample.

Astronomy & Astrophysics↗
DOE OSTI2023

A Predictive Prescription Framework for Stochastic Unit Commitment Using Boosting Ensemble Learning Algorithms

To take unit commitment (UC) decisions under uncertain load, most existing stochastic optimization (SO) frameworks adopt a generic representation of uncertainty. While load levels that materialize on a particular day are influenced by various covariates (such as the day of the week or temperature), SO frameworks typically disregard such side observations, wasting actionable information that could significantly enhance decision quality. Here, this article proposes a contextual SO (CSO) framework for UC under uncertain load, which can effectively exploit covariate observations in conjunction with a class of machine learning (ML) algorithms to improve the out-of-sample performance of UC decisions. It shows how three ML algorithms, adaptive boosting, gradient boosted trees, and extreme gradient boosting, can be used to this end, constituting the first application of these algorithms in any CSO framework. Using real-world data harvested from the New York ISO grid, we measure the out-of-sample performance of the framework in terms of total operation cost, shed load values, locational marginal prices, and total payments by the loads, against several benchmark methods proposed in the literature. The article has an online companion (Yurdakul et al.), wherein we present additional results and lay out further mathematical formulations used in this work.

42 ENGINEERING↗
DOE OSTI2024

Motivation and Design of the OCPP Security Service

Pacific Northwest National Laboratory is conducting in-depth research aimed at exploring how zero trust security principles can be effectively applied to electric vehicle charging infrastructure. This investigation seeks to enhance the resilience and reliability of these systems against cyber threats, ensuring secure and uninterrupted access to charging services for electric vehicle users and electric supply. Zero trust is a security concept centered on the belief that system operators should not automatically trust users or systems based on their location, whether inside or outside the organization, but instead must verify everything trying to connect to their systems before granting access. A key aspect of the project is to demonstrate and validate zero trust approaches targeted to electric vehicle (EV) charging infrastructure. It has been observed that both open-source and commercial solutions often overlook the specific protocols employed in managing EV charging stations and proceeded with a general, protocol-agnostic approach. While these strategies effectively block non-authorized routes to the charging infrastructure, they do not tackle the situations where attackers may exploit legitimate access channels, such as the inattentive operator model posited by the Idaho National Laboratory. To address this gap, this paper proposes and discusses a new security service targeted to the Open Charge Point Protocol (OCPP), which is the de facto protocol for the management of charging stations and serves a critical role in the broader adoption of electric vehicles. The design and architecture of the proposed OCPP security service are discussed in detail, outlining how it aims to safeguard charging station management system (CSMS) functions. The service is particularly important in scenarios where the charging station operator (CSO), responsible for the maintenance and operation of charging stations, and the charging network provider (CNP), which manages the charging network's accessibility and billing, are separate entities. This distinction is crucial because CSOs and CNPs often have different priorities, objectives, and operational responsibilities, which may not always align perfectly. For instance, a CSO might prioritize uptime and customer satisfaction, while a CNP might focus on maximizing revenue and network utilization. Such misalignment can create security vulnerabilities, as each entity might implement different policies and standards, potentially leaving gaps in the overall security posture.

33 ADVANCED PROPULSION SYSTEMS↗
NASA NTRS1994

Exotic fluoride molecules in IRC +10216: Confirmation of AlF and searches for MgF and CaF

Three new rotational transitions of aluminum fluoride (AlF) at 0.8 and 1.2 mm have been observed. The J = 10-9, J = 8-7, and J = 7-6 lines of AlF at 230, 263, and 329 GHz, respectively, were seen toward IRC +10216 using the Caltech Submillimter Observatory (CSO). Combined with the earlier data obtained for this species at IRAM at 2 and 3 mm, these measurements confirm the presence of the metal halide in this carbon-rich circumstellar shell. Analysis of the CSO and IRAM data suggests that AlF arises from a source with a diameter of theta(sub s) approximately = 5-10 sec and hence is present chiefly in the inner envelope of IRC +10216. In this region, the molecule has a column density of (0.3-1.1) x 10(exp 15)/sq cm, which indicates a fractional abundance of at least approximately 10(exp -9), relative to H2. Searches for the metal fluoride species CaF and MgF have also been conducted toward IRC +10216, but with negative results. The column density upper limits for MgF and CaF are N(sub tot) less than (1-4) x 10(exp 14)/sq cm. Relative abundances of these metal fluoride molecules can be understood in terms of chemical thermodynamic equilibrium. The presence of AlF in IRC +10216 also indicates that large quantities of fluorine must be present in the inner stellar envelope, suggesting that this element may be produced not primarily in explosive nucleosynthesis but rather in helium shell flashes, as indicated also by HF spectroscopy of red giant stars.

Ziurys, L. M.↗
NASA NTRS1998

New Molecular Species In Comet C/1995 (Hale-Bopp) Observed with the Caltech Submillimeter Observatory

We present millimeter-wave observations of HNCO, HC3N, SO, NH2CHO, H(13)CN, and H3O(+) in comet C/1995 O1 (Hale-Bopp) obtained in February-April, 1997 with the Caltech Submillimeter Observatory (CSO). HNCO, first detected at the CSO in comet C/1996 B2 (Hyakutake), is securely confirmed in comet Hale-Bopp via observations of three rotational transitions. The derived abundance with respect to H2O is (4-13) x 10(exp -4). HC3N, SO, and NH2CHO are detected for the first time in a comet. The fractional abundance of HC3N based on observations of three rotational lines is (1.9 +/- 0.2) x 10(exp -4). Four transitions of SO are detected and the derived fractional abundance, (2-8) x 10(exp -3), is higher than the upper limits derived from UV observations of previous comets. Observations of NH2CHO imply a fractional abundance of (1-8) x 10(exp -4). H3O(+) is detected for the first time from the ground. The H(13)CN (3-2) transition is also detected and the derived HCN/H(13)CN abundance ratio is 90 +/- 15, consistent with the terrestrial C-13/C-12 ratio. in addition, a number of other molecular species are detected, including HNC, OCS, HCO(+), CO(+), and CN (the last two are first detections in a comet at radio wavelengths).

Lis, D. C.↗
NASA NTRS2002

An Extremely Wide Bandwidth, Low-Noise SIS Heterodyne Receiver Design for Millimeter and Submillimeter Observations

Millimeter and submillimeter heterodyne receivers using state-of-the-art SIS detectors are capable of extremely large instantaneous bandwidths with noise temperatures within a few Kelvin of the quantum limit. We present the design for a broadband, sensitive, heterodyne spectrometer under development for the Caltech Submillimeter Observatory (CSO). The 180-300 GHz double-sideband design uses a single SIS device excited by a full bandwidth, fixed-tuned waveguide probe on a silicon substrate. The IF output frequency (limited by the MMIC low noise IF preamplifier) is 6-18 GHz, providing an instantaneous RF bandwidth of 24 GHz (double-sideband). The SIS mixer conversion loss should be no more than 1-2 dB with mixer noise temperatures across the band within 10 K of the quantum limit. The single-sideband receiver noise temperature goal is 70 K. The wide instantaneous bandwidth and low noise will result in an instrument capable of a variety of important astrophysical observations beyond the capabilities of current instruments. Lab testing of the receiver will begin in the summer of 2002, and the first use on the CSO should occur in the spring of 2003.

Sumner, Matthew↗