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DOE OSTI2021

Differences in Mechanism and Rate of Zeolite-Catalyzed Cyclohexanol Dehydration in Apolar and Aqueous Phase

The rate of acid-base catalyzed dehydration of alcohols strongly depends on the solvent and the environment of the acid sites. In this work, we find that Brønsted acidic sites in large-pore zeolites, but not in medium-pore zeolites, catalyze cyclohexanol dehydration in decalin at significantly higher rates than hydrated hydronium ions in aqueous phase. Specifically, the difference in turnover rates between the two solvents amounts to two to three orders of magnitude on H-BEA and H-FAU, while being very modest (within a factor of 2) for H-MFI. Combining kinetic, isotopic tracer and 2H NMR measurements, it is established that cyclohexanol dehydration generally follows an E1-elimination pathway in decalin. A notable exception is the monomer dehydration route on H-MFI, which exhibits a much lower activation energy and a substantially negative activation entropy that appear to be associated with an E2-type mechanism. The C-O bond cleavage displays a dominant degree of rate control in decalin, which stands in contrast to deprotonation (C-H cleavage) being rate-limiting in aqueous-phase dehydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys

Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while a clear effect of H 2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Unraveling the CO Oxidation Mechanism over Highly Dispersed Pt Single Atom on Anatase TiO 2 (101)

Catalysts with noble metals deposited as single atoms on metal oxide supports have recently been studied extensively due to their maximized metal utilization and potential for performing difficult chemical conversions owing to their unique electronic properties. Understanding of the reaction mechanisms on supported single-metal atoms is still limited but is highly important for designing more efficient catalysts. In this study, we report the complexity of the CO oxidation reaction mechanism on Pt single atoms supported on anatase TiO 2 (Pt SA /a-TiO 2 ) by coupling density functional theory (DFT) calculations and microkinetic analysis with kinetic measurements, in situ/operando infrared, and X-ray absorption spectroscopies. Starting from the adsorbed Pt SA occupying an O vacancy induced by reductive pretreatment, we show that CO oxidation follows a complex mechanism consisting of initiation steps to reorganize the active site and multibranch reactive cycles, with the Pt SA /a-TiO 2 catalyst not returning to its initial configuration. The initiation step consists of CO and O 2 adsorption healing the O vacancy, followed by CO oxidation using gas-phase CO to form Pt(CO). The reactive cycle alternates O 2 adsorption and dissociation to oxidize the catalyst to Pt(O)(O)(CO) and branching pathways of competing Langmuir–Hinshelwood (LH)- or Eley–Rideal (ER)-type CO oxidation steps to reduce it again to Pt(CO). In situ/operando infrared experiments, including cryogenic CO adsorption and isotopic CO exchange, confirm the combined involvement of strongly adsorbed CO and gas-phase CO in an Eley–Rideal step along the reaction cycle. Microkinetic modeling shows that Pt single atoms are present in a mixture of Pt(CO), Pt(CO)(O 2 ), Pt(O)(CO)(O 2 ), and Pt(CO)(CO 3 ) structures as the main intermediates during steady-state CO oxidation, all having the C–O vibrational stretch close to the experimentally observed value of 2115 cm –1 . Microkinetic modeling also shows that the fractional orders of CO and O 2 measured experimentally originate from multiple steps with a high degree of rate control and not from a simple competitive adsorption. The results demonstrate the complex reaction pathways that even CO oxidation on a simple single-atom system can follow, providing mechanistic insights for designing efficient Pt-based single-atom catalysts. Here, we further show that microkinetic modeling results are sensitive to changes in energies of intermediate and transition states within errors of density functional theory, which can ultimately lead to incorrect conclusions regarding the reaction pathways and most abundant reaction intermediates if not accounted for by experiments.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Platinum–Ruthenium Alloys Are Not Bifunctional CO Electro-Oxidation Catalysts: A Kinetic Analysis

Electro-oxidation of CO is a common kinetic bottleneck in many types of fuel cells and organic electrosynthesis processes. Alloys of Pt and Ru are often used as anode catalysts, with high activity attributed to bifunctionality; this suggests that Ru preferentially activates water to form surface hydroxyl groups that can react with Pt-bound CO. However, rigorous kinetic measurements have not confirmed this assertion under steady-state electro-oxidation conditions. Here, CO electro-oxidation is analyzed using several commercial Pt/C and Pt 100-x Ru x /C nanoparticle catalysts in acidic and alkaline electrolytes. Kinetic observables including apparent transfer coefficients and reaction orders are measured and evaluated using a degree of rate control analysis. The kinetic observables for both Pt and PtRu alloys are most consistent with competitive adsorption and Langmuir–Hinshelwood coupling across a single site-type, rather than two distinct sites. Furthermore, the role of Ru in CO electro-oxidation is assigned to be a purely electronic effect.

Alcohols↗

NASA NTRS1987

Telerobotic control of a dextrous manipulator using master and six-DOF hand-controllers for space assembly and servicing tasks

Two studies were conducted evaluating methods of controlling a telerobot; bilateral force reflecting master controllers and proportional rate six degrees of freedom (DOF) hand controllers. The first study compared the controllers on performance of single manipulator arm tasks, a peg-in-the-hole task, and simulated satellite orbital replacement unit changeout. The second study, a Space Station truss assembly task, required simultaneous operation of both manipulator arms (all 12 DOFs) and complex multiaxis slave arm movements. Task times were significantly longer and fewer errors were committed with the hand controllers. The hand controllers were also rated significantly higher in cognitive and manual control workload on the two-arm task. The master controllers were rated significantly higher in physical workload. There were no significant differences in ratings of manipulator control quality.

O'Hara, John M.↗

NASA NTRS1989

Control strategies for a telerobot

One of the major issues impacting the utility of telerobotic systems for space is the development of effective control strategies. For near-term applications, telerobot control is likely to utilize teleoperation methodologies with integrated supervisory control capabilities to assist the operator. Two different approaches to telerobotic control are evaluated: bilateral force reflecting master controllers and proportional rate six degrees-of-freedom hand controllers. The controllers' performance of single manipulator arm tasks is compared. Simultaneous operation of both manipulator arms and complex multiaxis slave arm movements is investigated. Task times are significantly longer and fewer errors are committed with the hand controllers. The hand controllers are also rated significantly higher in cognitive and manual control workload on the two-arm task. The master controllers are rated significantly higher in physical workload. The implications of these findings for space teleoperations and higher levels of control are discussed.

Ohara, John↗

NASA NTRS1985

Portable Temperature Set-Point Controller

Two off-the-shelf instruments combine to control chamber temperature over wide range. Portable controller for environmental test chambers changes temperatures automatically over range of -300 degrees to +400 degrees F (-184 degrees to + 204 degrees C). Unit controls rate of temperature change and time at given temperature. Controller developed to meet NASA Shuttle test requirements.

Milner, J. F.↗

NASA NTRS1993

Echocardiograms during six hours of bedrest at head-down and head-up tilt and during space flight

Left ventricular end-diastolic volume increased after 4 1/2 to 6 hours of space flight, but was significantly decreased after 5 to 6 days of space flight. To determine the role of acute gravitational effects in this phenomenon, responses to a 6-hour bedrest model of 0 gravity (G; 5 degrees head-down tilt) were compared with those of fractional gravity loads of 1/6 G, 1/3 G, and 2/3 G by using head-up tilts of 10 degrees, 20 degrees, and 42 degrees, respectively. On 4 different days, six healthy male subjects were tilted at one of the four angles for 6 hours. Cardiac dimensions and volumes were determined from two-dimensional and M-mode echocardiograms in the left lateral decubitus position at control (0), 2, 4, and 6 hours. Stroke volume decreased with time (P < .05) for all tilt angles when compared with control. Ejection fraction (EF) at -5 degrees was greater than at +20 degrees and +42 degrees (not significant); EF at +10 degrees was greater than at +42 degrees (not significant). For the tilt angles of -5 degrees, +10 degrees, and +20 degrees, mean heart rate decreased during the first 2 hours, and returned to control or was slightly elevated above control (+20 degrees) by 6 hours (not significant). At the +42 degrees angle of tilt, heart rate was increased above control at hours 2, 4, and 6. There were no significant differences in cardiac output at any time point for any tilt angle.(ABSTRACT TRUNCATED AT 250 WORDS).

Flight Experiment↗

DOE OSTI2020

DFT and microkinetic comparison of Pt, Pd and Rh-catalyzed ammonia oxidation

Ammonia oxidation is the heart of the Ostwald process and is important in emissions control. Catalytic behaviors are a function of conditions and are observed to vary across the platinum group metals (PGMs) Pt, Pd, Rh. Here, we combine density functional theory computations and microkinetic modeling to rationalize these dependencies. We compute reactions over model (2 1 1) and (1 1 1) surfaces of PGMs. Binding energies are similar on Pd and Pt and generally greater on Rh, while activation energies vary across all metals. Rates on (2 1 1) surfaces are greater than (1 1 1) surfaces. Additionally, the stepped Pt is most active and stepped Rh most selective to N 2 at ammonia slip conditions, while at Ostwald process conditions, stepped Pd is most active and stepped Pt most selective to NO. Degree of rate and selectivity control analysis provides insights into the reactions limiting performance of PGMs. Both activation barriers and surface coverages influence rates and selectivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Kinetics of the functionalization of mesoporous silica nanoparticles: Implications on surface group distributions, adsorption and catalysis

The post-synthesis functionalization (grafting) kinetics of mesoporous silica nanoparticles (MSN) with organotrimethoxysilanes (R-TMS) is studied via solution 1 H NMR spectroscopy. The process involves a rapid adsorption/ desorption pre-equilibrium followed by reaction of R-TMS with surface silanols. Grafting rates are affected by the functional group in R-TMS. For example, the grafting rate of aminopropyl-trimethoxysilane (AP-TMS) is one order of magnitude higher than other R-TMS. High concentrations of AP-TMS result in substrate-inhibition kinetics, likely due to steric and mobility constraints for reactant alignment at high coverage. The higher rates of AP-TMS grafting indicate a catalytic effect of amine groups. This effect depends on the amine’s basicity and can be used to control the grafting rates and degree of condensation of other R-TMS. Adjusting the rate of mercaptopropyl-trimethoxysilane (MP-TMS) grafting using amines gives MP-MSN materials of varying adsorptive and catalytic activities, illustrated by Pd scavenging experiments and use of Pd@MP-MSN as catalysts for a Suzuki-Miyaura cross-coupling reaction.

36 MATERIALS SCIENCE↗

NASA NTRS1984

An in flight investigation of pitch rate flight control systems and application of frequency domain and time domain predictive criteria

The degree of attitude control provided by current integral-proportional pitch rate command-type control systems, while a prerequisite for flared landing, is insufficient for 'Level 1' performance. The pilot requires 'surrogate' feedback cues to precisely control flight path in the landing flare. Monotonic stick forces and pilot station vertical acceleration are important cues which can be provided by means of angle-of-attack and pitch rate feedback in order to achieve conventional short period and phugoid characteristics. Integral-proportional pitch rate flight control systems can be upgraded to Level 1 flared landing performance by means of lead/lag and washout prefilters in the command path. Strong pilot station vertical acceleration cues can provide Level 1 flared landing performance even in the absence of monotonic stick forces.

Berthe, C. J.↗

NASA NTRS1993

Control of a serpentine manipulator with collision avoidance

The robotics lab at the Kennedy Space Center is investigating the possibility of using a 'serpentine' manipulator for Shuttle inspection and payload processing. Serpentine manipulators are characterized by a large number of degrees of freedom giving them a high degree of redundancy. This redundancy allows them to be used to reach confined areas while avoiding collisions with their environment. In this paper, the author describes a new approach to controlling the joint rates for an n degree of freedom robot such that it moves its end effector to a desired position while simultaneously avoiding collision of any part of the robot arm with obstacles. Joint rates which move the end effector toward the target are found via a Lyapunov stability function. The gradient of an obstacle cost function indicates the direction toward obstacle collision in the joint space. The component of the end effector joint rates orthogonal to the obstacle gradient becomes the commanded joint rates. A notional eleven DOF model is used to numerically demonstrate the efficacy of the control law.

Byers, Robert M.↗

NASA NTRS1990

Hand controller commonality evaluation process

A hand controller evaluation process has been developed to determine the appropriate hand controller configurations for supporting remotely controlled devices. These devices include remote manipulator systems (RMS), dexterous robots, and remotely-piloted free flyers. Standard interfaces were developed to evaluate six different hand controllers in three test facilities including dynamic computer simulations, kinematic computer simulations, and physical simulations. The hand controllers under consideration were six degree-of-freedom (DOF) position and rate minimaster and joystick controllers, and three-DOF rate controllers. Task performance data, subjective comments, and anthropometric data obtained during tests were used for controller configuration recommendations to the SSF Program.

Stuart, Mark A.↗

NASA NTRS2002

Baroreflex buffering and susceptibility to vasoactive drugs

BACKGROUND: The overall effect of vasoactive drugs on blood pressure is determined by a combination of the direct effect on vascular tone and an indirect baroreflex-mediated effect, a baroreflex buffering of blood pressure. Differences in baroreflex function affect the responsiveness to vasoactive medications, particularly baroreflex buffering of blood pressure; however, the magnitude is not known. METHODS AND RESULTS: We characterized baroreflex function and responses to vasoactive drugs in patients with idiopathic orthostatic intolerance, patients with essential hypertension, patients with monogenic hypertension and brachydactyly, patients with multiple system atrophy, and control subjects. We used phenylephrine sensitivity during ganglionic blockade as a measure of baroreflex buffering. Phenylephrine (25 microg) increased systolic blood pressure 6+/-1.6 mm Hg in control subjects, 6+/-1.1 mm Hg in orthostatic intolerance patients, 18+/-3.9 mm Hg in patients with essential hypertension, 31+/-3.4 mm Hg in patients with monogenic hypertension, and 25+/-3.4 mm Hg in patients with multiple system atrophy. Similar differences in sensitivities between groups were observed with nitroprusside. The sensitivity to vasoactive drugs was highly correlated with baroreflex buffering function and to a lesser degree with baroreflex control of heart rate. In control subjects, sensitivities to nitroprusside and phenylephrine infusions were correlated with baroreflex heart rate control and sympathetic nerve traffic. CONCLUSIONS: Our findings are consistent with an important effect of baroreflex blood pressure buffering on the sensitivity to vasoactive drugs. They suggest that even moderate changes in baroreflex function may have a substantial effect on the sensitivity to vasoactive medications.

NASA Discipline Regulatory Physiology↗

NASA NTRS2005

In Situ Electrochemical Deposition of Microscopic Wires

A method of fabrication of wires having micron and submicron dimensions is built around electrochemical deposition of the wires in their final positions between electrodes in integrated circuits or other devices in which the wires are to be used. Heretofore, nanowires have been fabricated by a variety of techniques characterized by low degrees of controllability and low throughput rates, and it has been necessary to align and electrically connect the wires in their final positions by use of sophisticated equipment in expensive and tedious post-growth assembly processes. The present method is more economical, offers higher yields, enables control of wire widths, and eliminates the need for post-growth assembly. The wires fabricated by this method could be used as simple electrical conductors or as transducers in sensors. Depending upon electrodeposition conditions and the compositions of the electroplating solutions in specific applications, the wires could be made of metals, alloys, metal oxides, semiconductors, or electrically conductive polymers. In this method, one uses fabrication processes that are standard in the semiconductor industry. These include cleaning, dry etching, low-pressure chemical vapor deposition, lithography, dielectric deposition, electron-beam lithography, and metallization processes as well as the electrochemical deposition process used to form the wires. In a typical case of fabrication of a circuit that includes electrodes between which microscopic wires are to be formed on a silicon substrate, the fabrication processes follow a standard sequence until just before the fabrication of the microscopic wires. Then, by use of a thermal SiO-deposition technique, the electrodes and the substrate surface areas in the gaps between them are covered with SiO. Next, the SiO is electron-beam patterned, then reactive-ion etched to form channels having specified widths (typically about 1 m or less) that define the widths of the wires to be formed. Drops of an electroplating solution are placed on the substrate in the regions containing the channels thus formed, then the wires are electrodeposited from the solution onto the exposed portions of the electrodes and into the channels. The electrodeposition is a room-temperature, atmospheric-pressure process. The figure shows an example of palladium wires that were electrodeposited into 1-mm-wide channels between gold electrodes.

Yun, Minhee↗

DOE OSTI2021

NO x adsorption with CO and C 2 H 4 on Pd/SSZ-13: Experiments and modeling

A transient monolith model containing microkinetic schemes for NO uptake and release over Pd/SSZ-13 without and with reductants CO or C2H4 is presented. The scheme involves three cationic Pd species (Z – [PdOH] + , Z – Pd 2+ Z – , Z – Pd + ) as the active sites during uptake of NO, CO and C 2 H 4 , and their desorption and conversion at higher temperature. Kinetic parameters are estimated through a combination of density functional theory (DFT) estimates and a fit of uptake, desorption and conversion data. The tuned model is validated at different uptake temperatures, ramp rates, and flowrates. A “degree of uptake control” parameter is defined that helps to identify the step(s) that are uptake controlling. The model helps to interpret the data features and is used to identify operating conditions to meet application-relevant performance metrics, including NO trapping efficiency and NO release temperature. Furthermore, the model demonstrates higher NO uptake on Pd/SSZ-13 compared to Pd/ZSM-5.

42 ENGINEERING↗

NASA NTRS1976

Investigation of selected disk systems

The large disk systems offered by IBM, UNIVAC, Digital Equipment Corporation, and Data General were examined. In particular, these disk systems were analyzed in terms of how well available operating systems take advantage of the respective disk controller's transfer rates, and to what degree all available data for optimizing disk usage is effectively employed. In the course of this analysis, generic functions and components of disk systems were defined and the capabilities of the surveyed disk system were investigated.

Source record↗

NASA NTRS2019

Water Storage and Transport Processes During Impact Experiments on Nominally Anhydrous Minerals

Water, in the form of structurally bound hydrogen in the crystal lattice of nominally anhydrous minerals (NAMs), strongly influences many important physical processes on terrestrial planets and planetary objects. Water enhances the rates of plastic deformation and controls the degree of partial melting in silicate rocks, which influences the generation of melt and therefore the nature of planetary volcanism. Water has also been experimentally demonstrated to influence the nature of lattice preferred orientation in deformed aggregates, and thus may be important in the interpretation of seismic anisotropy data collected from planetary bodies, such as from the current InSight mission on Mars. Therefore, much attention has been focused on characterizing the distribution and concentration of water in the planets and rocky bodies of our solar system.

Tielke, J.↗