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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRSDate not supplied

Bio-stasis: A Strategy for Survivability and Payload Cost Reduction in Long-duration Space Missions

As humans proceed with long-term space voyages, involving flights with lasting duration of months or years, “adaptation to space” will eventually lead to hard realities resultant physiological and psychological conditions must be realistically estimated and considered before it occurs. It is obvious that humans in their lifespan cannot adopt to spaceflight environment by reversible modification of their complex biochemical reactions and physiological functions without jeopardizing sustainable homeostasis shaped by multiple generations during evolution. In this case Nature offers an evolutionary proven alternative strategy- a coordinative adjustment of metabolism in order to survive. Incorporation of this metabolic adjustment strategy along with the relevant life support system into space flight architecture would protect humans during long term space flight from many irreversible physiological alterations and may dramatically reduce overall cost of space missions. In addition to the harmful space radiation and prolonged weightlessness, incorporation of this strategy may also benefit by solving other major medical unknowns in interplanetary flight such as isolation and psychological stress which still remains a risk. It is one of the priorities of NASA and other space agencies to figure out not only how to keep long-distance travelers alive and in good cognitive health but also how to return them to normal life on Earth with a minimum rehabilitation period after prolonged exposure to space. Presently re-adaptation of astronauts to Earth conditions and recovery from spaceflight exposure may take many months and years and, in some cases, require medical intervention. Therefore, recognizing physiological adjustment of the energy-regulating system as a viable life support strategy for human space exploration beyond LEO is essential.

Bio-stasis;↗
NASA NTRS2005

Vehicle Integrated Performance Analysis, the VIPA Experience: Reconnecting with Technical Integration

Today's NASA is facing significant challenges and changes. The Exploration initiative indicates a large increase in projects with limited increase in budget. The Columbia report has criticized NASA for its lack of insight and technical integration impacting its ability to provide safety. The Aldridge report is advocating NASA find new ways of doing business. Very early in the Space Launch Initiative (SLI) program a small team of engineers at MSFC were asked to propose a process for performing a system level assessment of a launch vehicle. The request was aimed primarily at providing insight and making NASA a "smart buyer." Out of this effort the VIPA team was created. The difference between the VIPA effort and many integration attempts is that VIPA focuses on using experienced people from various disciplines and a process which focuses them on a technically integrated assessment. Most previous attempts have focused on developing an all encompassing software tool. In addition, VIPA anchored its process formulation in the experience of its members and in early developmental Space Shuttle experience. The primary reference for this is NASA-TP-2001-210092, "Launch Vehicle Design Process: Characterization, Technical Integration, and Lessons Learned," and discussions with its authors. The foundations of VIPA's process are described. The VIPA team also recognized the need to drive detailed analysis earlier in the design process. Analyses and techniques typically done in later design phases, are brought forward using improved computing technology. The intent is to allow the identification of significant sensitivities, trades, and design issues much earlier in the program. This process is driven by the T-model for Technical Integration described in the aforementioned reference. VIPA's approach to performing system level technical integration is discussed in detail. Proposed definitions are offered to clarify this discussion and the general systems integration dialog. VIPA's capabilities and process can now be used to significantly enhance the development and monitoring of realizable project requirements. This is done through the use of VIPA's V-model. Starting with a given concept, VIPA's assessment validates the concept's stated performance, identifies significant issues either with the concept or the requirements, and then re-integrates these issues to determine impacts. This process is discussed along with a description of how it may be integrated into a program's insight and review process. The VIPA process has been employed successfully on several projects including SLI, Orbital Space Plane (OSP), and several heavy lift concepts for Exploration. It has also been proposed for use on the Jupiter Icy Moon (JIMO) spacecraft. The VIPA process has gained favor with both engineering and project organizations for being responsive and insightful. Selected results from these assessments will be presented.

McGhee, David S.↗
NASA NTRS1999

Investigation of the Large Scale Evolution and Topology of Coronal Mass Ejections in the Solar Wind

This investigation is concerned with the large-scale evolution and topology of Coronal Mass Ejections (CMEs) in the solar wind. During this reporting period we have analyzed a series of low density intervals in the ACE (Advanced Composition Explorer) plasma data set that bear many similarities to CMEs. We have begun a series of 3D, MHD (Magnetohydrodynamics) coronal models to probe potential causes of these events. We also edited two manuscripts concerning the properties of CMEs in the solar wind. One was re-submitted to the Journal of Geophysical Research.

Riley, Peter↗
NASA NTRS2010

Low-Cost Propellant Launch to LEO from a Tethered Balloon - Economic and Thermal Analysis

This paper provides new analysis of the economics of low-cost propellant launch coupled with dry hardware re-use, and of the thermal control of the liquid hydrogen once on-orbit. One conclusion is that this approach enables an overall reduction in the cost-permission by as much as a factor of five as compared to current approaches for human exploration of the moon, Mars, and near-Earth asteroids.

Wilcox, Brian H.↗
NASA NTRS2019

Towards Resilient Autonomous Navigation of Drones

Robots and particularly drones are especially useful in exploring extreme environments that pose hazards to humans. To ensure safe operations in these situations, usually perceptually degraded and without good GNSS, it is critical to have a reliable and robust state estimation solution. The main body of literature in robot state estimation focuses on developing complex algorithms favoring accuracy. Typically, these approaches rely on a strong underlying assumption: the main estimation engine will not fail during operation. In contrast, we propose an architecture that pursues robustness in state estimation by considering redundancy and heterogeneity in both sensing and estimation algorithms. The architecture is designed to expect and detect failures and adapt the behavior of the system to ensure safety. To this end, we present HeRO (Heterogeneous Redundant Odometry): a stack of estimation algorithms running in parallel supervised by a resiliency logic. This logic carries out three main functions: a) perform confidence tests both in data quality and algorithm health; b) re-initialize those algorithms that might be malfunctioning; c) generate a smooth state estimate by multiplexing the inputs based on their quality. The state and quality estimates are used by the guidance and control modules to adapt the mobility behaviors of the system. The validation and utility of the approach are shown with real experiments on a ying robot for the use case of autonomous exploration of subterranean environments, with particular results from the STIX event of the DARPA Subterranean Challenge.

Agha-mohammadi, Ali-akbar↗
NASA NTRS2012

Hybrid Collaborative Learning for Classification and Clustering in Sensor Networks

Traditionally, nodes in a sensor network simply collect data and then pass it on to a centralized node that archives, distributes, and possibly analyzes the data. However, analysis at the individual nodes could enable faster detection of anomalies or other interesting events as well as faster responses, such as sending out alerts or increasing the data collection rate. There is an additional opportunity for increased performance if learners at individual nodes can communicate with their neighbors. In previous work, methods were developed by which classification algorithms deployed at sensor nodes can communicate information about event labels to each other, building on prior work with co-training, self-training, and active learning. The idea of collaborative learning was extended to function for clustering algorithms as well, similar to ideas from penta-training and consensus clustering. However, collaboration between these learner types had not been explored. A new protocol was developed by which classifiers and clusterers can share key information about their observations and conclusions as they learn. This is an active collaboration in which learners of either type can query their neighbors for information that they then use to re-train or re-learn the concept they are studying. The protocol also supports broadcasts from the classifiers and clusterers to the rest of the network to announce new discoveries. Classifiers observe an event and assign it a label (type). Clusterers instead group observations into clusters without assigning them a label, and they collaborate in terms of pairwise constraints between two events [same-cluster (mustlink) or different-cluster (cannot-link)]. Fundamentally, these two learner types speak different languages. To bridge this gap, the new communication protocol provides four types of exchanges: hybrid queries for information, hybrid "broadcasts" of learned information, each specified for classifiers-to-clusterers, and clusterers-to-classifiers. The new capability has the potential to greatly expand the in situ analysis abilities of sensor networks. Classifiers seeking to categorize incoming data into different types of events can operate in tandem with clusterers that are sensitive to the occurrence of new kinds of events not known to the classifiers. In contrast to current approaches that treat these operations as independent components, a hybrid collaborative learning system can enable them to learn from each other.

Wagstaff, Kiri L.↗
NASA NTRS2013

Application Agreement and Integration Services

Application agreement and integration services are required by distributed, fault-tolerant, safety critical systems to assure required performance. An analysis of distributed and hierarchical agreement strategies are developed against the backdrop of observed agreement failures in fielded systems. The documented work was performed under NASA Task Order NNL10AB32T, Validation And Verification of Safety-Critical Integrated Distributed Systems Area 2. This document is intended to satisfy the requirements for deliverable 5.2.11 under Task 4.2.2.3. This report discusses the challenges of maintaining application agreement and integration services. A literature search is presented that documents previous work in the area of replica determinism. Sources of non-deterministic behavior are identified and examples are presented where system level agreement failed to be achieved. We then explore how TTEthernet services can be extended to supply some interesting application agreement frameworks. This document assumes that the reader is familiar with the TTEthernet protocol. The reader is advised to read the TTEthernet protocol standard [1] before reading this document. This document does not re-iterate the content of the standard.

Driscoll, Kevin R.↗
NASA NTRS2013

Autonomous Vision-Based Tethered-Assisted Rover Docking

Many intriguing science discoveries on planetary surfaces, such as the seasonal flows on crater walls and skylight entrances to lava tubes, are at sites that are currently inaccessible to state-of-the-art rovers. The in situ exploration of such sites is likely to require a tethered platform both for mechanical support and for providing power and communication. Mother/daughter architectures have been investigated where a mother deploys a tethered daughter into extreme terrains. Deploying and retracting a tethered daughter requires undocking and re-docking of the daughter to the mother, with the latter being the challenging part. In this paper, we describe a vision-based tether-assisted algorithm for the autonomous re-docking of a daughter to its mother following an extreme terrain excursion. The algorithm uses fiducials mounted on the mother to improve the reliability and accuracy of estimating the pose of the mother relative to the daughter. The tether that is anchored by the mother helps the docking process and increases the system's tolerance to pose uncertainties by mechanically aligning the mating parts in the final docking phase. A preliminary version of the algorithm was developed and field-tested on the Axel rover in the JPL Mars Yard. The algorithm achieved an 80% success rate in 40 experiments in both firm and loose soils and starting from up to 6 m away at up to 40 deg radial angle and 20 deg relative heading. The algorithm does not rely on an initial estimate of the relative pose. The preliminary results are promising and help retire the risk associated with the autonomous docking process enabling consideration in future martian and lunar missions.

Axel docking↗
NASA NTRS2017

Calibrating the IXPE Observatory from Ground to Space

The Imaging X-ray Polarimetry Explorer (IXPE) will be the next SMEX mission launched by NASA in 2021 in collaboration with the Italian Space Agency (ASI). IXPE will perform groundbreaking measurements of imaging polarization in X-rays for a number of different classes of sources with three identical telescopes, finally (re)opening a window in the high energy Universe after more than 40 years since the first pioneering results. The unprecedented sensitivity of IXPE to polarization poses peculiar requirements on the payload calibration, e.g. the use of polarized and completely unpolarized radiation, both on ground and in orbit, and can not rely on a systematic comparison with results obtained by previous observatories. In this paper, we will present the IXPE calibration plan, describing both calibrations which will be performed on the detectors at INAF-IAPS in Rome (Italy) and the calibration on the mirror and detector assemblies which will be carried out at Marshall Space Flight Center in Huntsville, Alabama. On orbit calibrations, performed with calibrations sources mounted on a filter wheel and placed in front of each detector when necessary, will be presented as well.

X-ray astronomy Polarimetry Calibratio↗
NASA NTRSDate not supplied

Modular Open Systems Approach (MOSA) for a Robust Commercial Lunar Ecosystem

Modular Open Systems Approaches (MOSAs) have been adopted worldwide to solve a myriad of challenges. Open systems by their nature maximize accessibility, reduce barriers to entry, and prevent vendor lock. Similarly, modularity speeds innovation, fosters design re-use, and enables incremental development & growth. Architectures developed using a MOSA synergize the benefits of modularity and open systems to produce better products at lower developmental cost and risk, saving the consumer money while allowing greater developer profit margins. Specific to the challenge of lunar exploration, a MOSA will ensure interoperability among diverse commercial, government, and international partners. Complex spaceflight systems can be assembled, upgraded, and serviced far more easily and with greater commercial involvement with the use of a MOSA. By allowing partners to self-limit their scope to key strengths, they can focus on producing premier components without carrying the high risk and associated cost of auxiliary tasks they don’t specialize in. We survey commercial and Department of Defense (DoD) lessons learned in past decades, discuss DoD robotics’ experience in Iraq and Afghanistan (first without then with MOSAs), and analyze the flourishing commercial ecosystem that has resulted from DoD MOSA adoption. We explore the future of lunar operations to demonstrate the criticality of MOSA adoption in key areas at the right time. Two specific lunar technical fields are studied as examples: Power and In-Situ Resource Utilization (ISRU). Finally, recognizing that the lunar ISRU campaign will be an eminently collaborative operation requiring seamless partnering among diverse commercial, government, and international partners, a comprehensive technology development ecosystem is explored aimed at enabling ISRU in a way that systems and components are affordable for commercial partners to design, build, and sustain.

Mathew DeMinico↗
DOE OSTI2024

Recycling of CF-ABS machining waste for large format additive manufacturing

Large format additive manufacturing (LFAM) necessitates the use of short fiber thermoplastic composites, such as carbon fiber filled acrylonitrile butadiene styrene, to enable printing. Currently, when LFAM parts are machined into their final shape, the machining scrap (i.e., small flake like particles and offcuts) is landfilled. Previous studies have demonstrated the viability of recycling end-of-life LFAM parts by shredding and optionally re-compounding the material back into pellets. However, there is little understanding of the value and performance of recycled material made from LFAM machining scrap, which if pursued could motivate more broad recycling of this waste stream. In this study, recycled in-process machining scrap is explored as an LFAM feedstock source. Herein, it is found that the primary degradation mechanism of the recycled material is significant fiber length attrition during surface machining. While this fiber attrition negatively impacts the mechanical performance of the material in the print direction, it seems that the changes in processing behaviors and print quality, namely the surface roughness of the printed structure associated with shorter fiber lengths, is beneficial to interlayer adhesion. The tensile strength and elastic modulus of the recycled material, in the print direction, decreased 11% and 31% respectively compared to the pristine material. However, in the layer-wise direction it was found that the recycled material exhibited no significant change in elastic modulus and a significant 21% increase in tensile strength – a surprising result. In conclusion, this work indicates that machining waste could be a viable material stream for recycled LFAM feedstock materials.

42 ENGINEERING↗
NASA NTRS2011

Development of the Orion Crew Module Static Aerodynamic Database: Hypersonic - Part 1

The Orion aerodynamic database provides force and moment coefficients given the velocity, attitude, configuration, etc. of the Crew Exploration Vehicle (CEV). The database is developed and maintained by the NASA CEV Aerosciences Project team from computational and experimental aerodynamic simulations. The database is used primarily by the Guidance, Navigation, and Control (GNC) team to design vehicle trajectories and assess flight performance. The initial hypersonic re-entry portion of the Crew Module (CM) database was developed in 2006. Updates incorporating additional data and improvements to the database formulation and uncertainty methodologies have been made since then. This paper details the process used to develop the CM database, including nominal values and uncertainties, for Mach numbers greater than 8 and angles of attack between 140deg and 180deg. The primary available data are more than 1000 viscous, reacting gas chemistry computational simulations using both the Laura and Dplr codes, over a range of Mach numbers from 2 to 37 and a range of angles of attack from 147deg to 172deg. Uncertainties were based on grid convergence, laminar-turbulent solution variations, combined altitude and code-to-code variations, and expected heatshield asymmetry. A radial basis function response surface tool, NEAR-RS, was used to fit the coefficient data smoothly in a velocity-angle-of-attack space. The resulting database is presented and includes some data comparisons and a discussion of the predicted variation of trim angle of attack and lift-to-drag ratio. The database provides a variation in trim angle of attack on the order of +/-2deg, and a range in lift-to-drag ratio of +/-0.035 for typical vehicle flight conditions.

Bibb, Karen L.↗
NASA NTRS2018

Special Topic for Nuclear CLT: Kilopower Project

NASA needs nuclear power to achieve a sustainable human presence on Lunar and Mars surfaces. Kilopower II addresses a gap in the NASA Technology Roadmaps (TA-03) for robust, sun-independent power generation in the 1 to 10 kWe range. NASA needs a long-life, low-cost power option for missions where solar is not practical. Future Exploratory Missions require a reliable source of power Lunar/Mars explorations including ISRU propellant production and crew life support and operations, for which there is no off-the-shelf solution. KRUSTY serves as a baseline for on follow-on human missions with multiple stand-alone units that provide redundancy/fault tolerance and flexibility for re-use at multiple sites with power needs of 1 to 10 kWe throughout the solar system (e.g. permanently-shaded lunar craters, subsurface Europa science, deep space electric propulsion, others.)

Hernandez-Lugo, Dionne Marie↗
NASA NTRS2000

Relativistic Astrophysics in Black Hole and Low-Mass Neutron Star Binaries LTSA98

My group, in close collaboration with Dr. Zhang's group at University of Alabama-Huntsville, have been systematically analyzing and re-analyzing a substantial amount of archival data from previous and ongoing X-ray missions, in order to study possible relativistic effects around stellar-mass black holes and neutron stars. Our effort has been focused primarily on the data from the Rossi X-ray Timing Explorer. We carefully studied interesting quasi-periodic X-ray variability in newly discovered black hole candidates (XTE J1859+226 and XTE J1550-564), which, as we had proposed earlier, could be caused by general relativistic process (e.g., frame dragging) around the central black hole. We also discovered an intriguing temporal correlation between X-ray photons at different energies that is associated with the quasi-periodic signals of interest. The results provided new insights into the physical origin of the phenomena. Furthermore, we studied the spectral lines of black hole candidates which provide another avenue for studying general relativistic processes around black holes. The lines-may originate in the relativistic jets (which could be powered by the spin of the black hole) or in the disk around the black hole, as in the cases of 4U 1630-47 and GX 339-4 (two well-known black hole candidates), and may thus be distorted or shifted due to relativistic effects. Of course, neutron star systems were not forgotten either. After examining the properties of newly discovered fast quasi-periodic variability (at kiloHertz) associated with such systems, we proposed a relativistic model to explain the origin of the signals. We have also started to use new great observatories in orbit (such as Chandra and XMM-Newton) to observe the sources that are of interest to us. Finally, interesting results were also been obtained from our collaborations with other groups who are interested in some of the same objects. Such collaborative efforts have greatly enhanced the project and will likely continue in the future.

Cui, Wei↗
NASA NTRS2013

Orion GNC Mitigation Efforts for Van Allen Radiation

The Orion Crew Module (CM) is NASA's next generation manned space vehicle, scheduled to return humans to lunar orbit in the coming decade. The Orion avionics and GN&C architectures have progressed through a number of project phases and are nearing completion of a major milestone. The first unmanned test mission, dubbed "Exploration Flight Test One" (EFT-1) is scheduled to launch from NASA Kennedy Space Center late next year and provides the first integrated test of all the vehicle systems, avionics and software. The EFT-1 mission will be an unmanned test flight that includes a high speed re-entry from an elliptical orbit, which will be launched on an expendable launch vehicle (ELV). The ELV will place CM and the ELV upper stage into a low Earth orbit (LEO) for one revolution. After the first LEO, the ELV upper stage will re-ignite and place the combined upper stage/CM into an elliptical orbit whose perigee results in a high energy entry to test CM response in a relatively high velocity, high heating environment. While not producing entry velocities as high as those experienced in returning from a lunar orbit, the trajectory was chosen to provide higher stresses on the thermal protection and guided entry systems, as compared against a lower energy LEO entry. However the required entry geometry with constraints on inclination and landing site result in a trajectory that lingers for many hours in the Van Allen radiation belts. This exposes the vehicle and avionics to much higher levels of high energy proton radiation than a typical LEO or lunar trajectory would encounter. As a result, Van Allen radiation poses a significant risk to the Orion avionics system, and particularly the Flight Control Module (FCM) computers that house the GN&C flight software. The measures taken by the Orion GN&C, Flight Software and Avionics teams to mitigate the risks associated with the Van Allen radiation on EFT-1 are covered in the paper. Background on the Orion avionics subsystem is provided, as well as an overview of the GN&C software architecture. The measures taken to handle radiation induced failure of the one or both of the FCM's are presented, and finally simulation and actual hardware-in-the-loop (HWIL) results are shown confirming the validity of the implementation. The paper presents an overview of the Orion avionics architecture describing the GNC sensors, onboard data network as well as the flight control computers and their planned restart capabilities. GN&C sensors include two Orion Inertial Measurement Units (OIMU's), a Vision Processing Unit (VPU) to process camera images, three barometric altimeters and a single GPS receiver. All of the sensors communicate to one of two Power and Data Units (PDU's). The PDU's multiplex analog and serial data from the sensors and write the data to the Orion Data Network (ODN). The OIMU s write measurement messages directly as onto the ODN, but they are routed through PDU network switches.

King, Ellis T.↗
NASA NTRS2018

Priority Science Targets for Future Sample Return Missions Within the Inner Solar System Out to the Year 2061

The Astromaterials Acquisition and Curation Office at NASA Johnson Space Center (JSC) is re-sponsible for curating all of NASA's extraterrestrial samples. The NASA Curation Office plans for the requirements of future collections in an ''Advanced Curation'' program. Advanced Curation is tasked with developing procedures, technology, and data sets necessary for curating new types of collections as envisioned by NASA exploration goals. Here we review the science value of some potential targets for sample return missions from the inner solar system over the next 43 years.

McCubbin, F. M.↗
NASA NTRS2018

Design Optimisation and Mass Saving of the Structure of the Orion-MPCV European Service Module

This paper presents an overview of the design optimisation measures that have been proposed and analysed in order to reduce the mass of the structure, including the MMOD (Micro-Meteoroid and Orbital Debris) protection system, of the ESM (European Service Module) for the “Orion” MPCV (Multi-Purpose Crew Vehicle). Under an agreement between NASA and ESA, the NASA Orion MPCV for human space exploration missions will be powered by a European Service Module, based on the design and experience of the ATV (Automated Transfer Vehicle). The development and qualification of the European Service Module is managed and implemented by ESA. The ESM prime contractor and system design responsible is Airbus Defence and Space. Thales Alenia Space Italia is responsible for the design and integration of the ESM Structure and MMOD protection system in addition to the Thermal Control System and the Consumable Storage System. The Orion Multi-Purpose Crew Vehicle is a pressurized, crewed spacecraft that transports up to four crew members from the Earth’s surface to a nearby destination or staging point. Orion then brings the crew members safely back to the Earth’s surface at the end of the mission. Orion provides all services necessary to support the crew members while on-board for short duration missions (up to 21 days) or until they are transferred to another orbiting habitat. The ESM supports the crew module from launch through separation prior to re-entry by providing: in-space propulsion capability for orbital transfer, attitude control, and high altitude ascent aborts; water and oxygen/nitrogen needed for a habitable environment; and electrical power generation. In addition, it maintains the temperature of the vehicle's systems and components and offers space for unpressurized cargo and scientific payloads. The ESM has been designed for the first 2 Lunar orbit missions, EM-1 (Exploration mission 1) is an un-crewed flight planned around mid-2020, and EM-2, the first crewed flight, is planned in 2022. At the time where the first ESM is about to be weighted, the predicted mass lies slightly above the initial requirement. For future builds, mass reduction of the Service Module has been considered necessary. This is being investigated, together with other design improvements, in order to consolidate the ESM design and increase possible future missions beyond the first two Orion MPCV missions. The mass saving study has introduced new optimised structural concepts, optimisation of the MMOD protection shields, and optimised redesign of parts for manufacturing through AM (Additive Manufacturing).

Micro-Meteroids and Orbital Debris Protection Syst↗
NASA NTRS2016

Relating FTS Catalyst Properties to Performance

During the reporting period June 23, 2011 to August 31, 2013, CAER researchers carried out research in two areas of fundamental importance to the topic of cobalt-based Fischer-Tropsch Synthesis (FTS): promoters and stability. The first area was research into possible substitute promoters that might be used to replace the expensive promoters (e.g., Pt, Re, and Ru) that are commonly used. To that end, three separate investigations were carried out. Due to the strong support interaction of γ-Al2O3 with cobalt, metal promoters are commonly added to commercial FTS catalysts to facilitate the reduction of cobalt oxides and thereby boost active surface cobalt metal sites. To date, the metal promoters examined have been those up to and including Group 11. Because two Group 11 promoters (i.e., Ag and Au) were identified to exhibit positive impacts on conversion, selectivity, or both, research was undertaken to explore metals in Groups 12 - 14. The three metals selected for this purpose were Cd, In, and Sn. At a higher loading of 25%Co on alumina, 1% addition of Cd, In, or Sn was found to-on average-facilitate reduction by promoting a heterogeneous distribution of cobalt consisting of larger lesser interacting cobalt clusters and smaller strongly interacting cobalt species. The lesser interacting species were identified in TPR profiles, where a sharp low temperature peak occurred for the reduction of larger, weakly interacting, CoO species. In XANES, the Cd, In, and Sn promoters were found to exist as oxides, whereas typical promoters (e.g., Re, Ru, Pt) were previously determined to exist in an metallic state in atomic coordination with cobalt. The larger cobalt clusters significantly decreased the active site density relative to the unpromoted 25%Co/Al2O3 catalyst. Decreasing the cobalt loading to 15%Co eliminated the large non-interacting species. The TPR peak for reduction of strongly interacting CoO in the Cd promoted catalyst occurred at a measurably lower temperature than in the unpromoted catalyst. Nevertheless, the Co clusters remained slightly larger, on average, in comparison with the unpromoted 15%Co/Al2O3 reference catalyst. None of the promoted catalysts (i.e., with Cd, In, or Sn) exhibited surface Co0 site densities higher than that of the unpromoted catalyst. In activity testing, the activities were even much lower than what was expected from the H2-TPD results. Two possible explanations were proposed: (1) the promoters may be located on the surfaces of cobalt particles, blocking surface Co0 but being able to desorb hydrogen or (2) the promoters may facilitate Co oxidation during FTS, as previously observed by Huffman and coworkers when K was added to cobalt catalysts.

Zirconia↗