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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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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Supportability Challenges, Metrics, and Key Decisions for Future Human Spaceflight

Future crewed missions beyond Low Earth Orbit (LEO) represent a logistical challenge that is unprecedented in human space flight. Astronauts will travel farther and stay in space for longer than any previous mission, far from timely abort or resupply from Earth. Under these conditions, supportability { defined as the set of system characteristics that influence the logistics and support required to enable safe and effective operations of systems { will be a much more significant driver of space system lifecycle properties than it has been in the past. This paper presents an overview of supportability for future human space flight. The particular challenges of future missions are discussed, with the differences between past, present, and future missions highlighted. The relationship between supportability metrics and mission cost, performance, schedule, and risk is also discussed. A set of pro- posed strategies for managing supportability is presented (including reliability growth, uncertainty reduction, level of repair, commonality, redundancy, In-Space Manufacturing (ISM) (including the use of material recycling and In-Situ Resource Utilization (ISRU) for spares and maintenance items), reduced complexity, and spares inventory decisions such as the use of predeployed or cached spares - along with a discussion of the potential impacts of each of those strategies. References are provided to various sources that describe these supportability metrics and strategies, as well as associated modeling and optimization techniques, in greater detail. Overall, supportability is an emergent system characteristic and a holistic challenge for future system development. System designers and mission planners must carefully consider and balance the supportability metrics and decisions described in this paper in order to enable safe and effective beyond-LEO human space flight.

Owens, Andrew C.↗
NASA NTRSDate not supplied

Metrics in Space Life Support Technology Selection

Engineering metrics are useful in space life support technology selection, but they must be carefully used. Metrics are only part of a complete system trade-off. Metrics do harm if they cause neglect of other important technical, organizational, or intuitive decision factors. Two metrics have damaged space life support, closure and Equivalent Systems Mass (ESM). Closure measures the fraction of the required system inputs that are produced by recycling system outputs. Increasing closure produces diminishing returns and becomes increasingly expensive. Increasing closure does not directly contribute to providing better life support. ESM measures the total launch mass required to provide life support. ESM includes the mass of the system hardware and of its power, cooling, pressurized volume, spares, and logistics. ESM predicts launch costs, but recently launch costs have been reduced by a factor of 20 or more. System development cost for space hardware is often much greater than launch cost. The past nearly exclusive use of ESM has led to the neglect of Life Cycle Cost (LCC), reliability, cost, and the other engineering factors. Closure and ESM have misguided space life support technology selection for more than twenty years and have adversely affected the expenditure of 100’s of millions of dollars. Metrics can be effectively used three ways in space life support technology selection: 1. A small set of key engineering metrics for preliminary screening. 2. A full set of engineering to guide technical selection. 3. Combining engineering metrics with organizational, political, and intuitive decision factors to understand technology selection. The past emphasis on closure and ESM served to support recycling life support over resupply and built on the intuitive appeal of a human ecosystem in space.

Harry W Jones↗
NASA NTRSDate not supplied

The Effective Use of Metrics in Space Life Support System Trade-Offs

Engineering metrics are useful in space life support technology selection, but they must be carefully used. Metrics are only part of a complete system trade-off. Metrics do harm if they cause neglect of other important technical, organizational, or intuitive decision factors. Two metrics have damaged space life support, closure and Equivalent Systems Mass (ESM). Closure measures the fraction of the required system inputs that are produced by recycling system outputs. Increasing closure produces diminishing returns and becomes increasingly expensive. Increasing closure does not directly contribute to providing better life support. ESM measures the total launch mass required to provide life support. ESM includes the mass of the system hardware and of its power, cooling, pressurized volume, spares, and logistics. ESM predicts launch costs, but recently launch costs have been reduced by a factor of 20 or more. System development cost for space hardware is often much greater than launch cost. The past nearly exclusive use of ESM has led to the neglect of Life Cycle Cost (LCC), reliability, cost, and the other engineering factors. Closure and ESM have misguided space life support technology selection for more than twenty years and have adversely affected the expenditure of 100’s of millions of dollars. Metrics can be effectively used three ways in space life support technology selection: 1. A small set of key engineering metrics for preliminary screening. 2. A full set of engineering to guide technical selection. 3. Combining engineering metrics with organizational, political, and intuitive decision factors to understand technology selection. The past emphasis on closure and ESM served to support recycling life support over resupply and built on the intuitive appeal of a human ecosystem in space.

Harry W. Jones↗
NASA NTRSDate not supplied

Crew Performance Support System to Aid in Anomaly Resolution: Concept of Operations

As missions progress into deep space, communication delays and disruptions will disenable the crew’s reliance on Earth experts. There are also limitations in the amount of data that can be downlinked to the ground. It is prudent to assume that critical, complex vehicle or habitat sub-systems will malfunction at a time when a lunar or Mars’ crew cannot rely on the Earth-Support team to detect, diagnose and resolve the problem and it is impractical to expect a small crew to step-in with the same level of expertise as 50+ authorities. The crew will need novel processes and advanced technological support to independently identify and resolve safety- and time-critical anomalies. That a self-reliant crew is unable to respond appropriately to time-critical anomalies is a significant risk to crew safety and mission success. This risk is driven by several factors; novel and unanticipated anomalies would not have been trained pre-flight, the crew could forget their pre-flight training or spaceflight stressors could impair the crew’s problem-solving ability. At last year’s IWS, Beard reported that a single spaceflight stressor (elevated CO2) could undermine the crew’s ability to independently respond to emergencies. Concept of Operations (ConOps) provide a common view of future system functions to all stakeholders. For the current project, a ConOps was developed that describes the operational processes, practices and capabilities needed by a crew of astronauts on deep space missions to autonomously respond to anticipated and unanticipated anomalies. It is crucial to recognize that, as of August 2018 existing technologies are unable to effectively support crew anomaly response to unanticipated events. “Intelligent technology” has not reached a maturity level that permits generalizing a solution to novel situations. For example, to train intelligent technology requires volumes of data that do not exist. The complexities involved in a manned mission to Mars cannot be compared to sending rovers to Mars using scripted software. This ConOps proposes a Crew Performance Support System (CPSS) that will push NASA and its industry partners toward what will be required for a safe and successful manned mission to Mars. Anomaly resolution during a deep space mission will take place within a dynamic, or changing, context. The figure to the left shows five broad contextual variables: the organizational culture, mission context, system characteristics, team characteristics and individual characteristics. The yellow arrow indicates that spaceflight and task-related stressors can affect system, team and individual crewmember characteristics and therefore anomaly response potential. The figure depicts a protective umbrella of Human-System Integration (HSI) principles that should be instituted during CPSS development including a balanced workload, shared situation awareness and building an appropriate level of trust in the automation. The figure also depicts two interrelated and cooperative components, an HSI Data System and other Enabling Capabilities will be required to support crew anomaly response and Earth-Support situation awareness. As we journey from ISS to Gateway to Mars, multiple, simultaneous and integrated research and development efforts (i.e., support systems co-evolution) must be implemented to meet the problem-solving challenges a self-reliant crew will face on a Mars’ mission. The crossovers between the capabilities are just as important as the discrete capabilities themselves. As the capabilities mature, the lines between the support subdomains will blur and an integrated system will emerge. The ConOps summarizes current knowledge about how highly trained people solve anomalies in safety- and time-critical situations, describes a group of capabilities that could help to reduce the extant risk and documents requirements levied on additional systems that provides critical inputs to the CPSS. Scenarios are used to promote a shared understanding of processes, practices and technological goals needed for safe and productive manned missions beyond LEO.

HSIA risk↗
NASA NTRSDate not supplied

Examining the Trends in Financial Support Given to Science Teams for Data Analysis in Mission Proposals

Introduction: The goal of this summer internship research project was to analyze trends in financial support proposed for the science teams of planetary missions. The analysis focuses on the funding for Co-Investigators (Co-Is) to conduct research and/or data analysis needed to achieve the science objectives of the mission. The operational portion of the missions after launch (i.e., Phase E, including cruise and prime operations at the final destination) were examined since that is when the bulk of research is funded and conducted. The objectives of the project were to determine the average level of support for Co-Investigators, identify variation between mission competitions and over time, and determine the relationship between mission type and the amount of support requested. Methodology: This project was conducted using data from 90 proposals submitted to six mission competitions in the Discovery and New Frontiers programs. The level of support for Co-Is was determined by examining Work Breakdown Structure (WBS) 4 (Science Analysis) for Phase E, which was further subdivided into cruise and prime operations. This data represents a proxy rather than the actual funding Co-Is receive to perform research and data analysis because not every dollar in WBS 4 is spent on this activity. Therefore, the proxy obtained in this research represents an overestimate of the funds allocated to Co-Is for research and data analysis. Findings: Analysis shows that on average a Co-I receives approximately four full years of support spread across the entirety of Phase E for science analysis. The variation among proposed missions is less than expected given the variety of factors that are expected to drive this metric (length of mission, mission type, etc.). Additionally, the level of requested support for Co-Is has been remarkably consistent across every variable considered (by competition, over time, by mission type) over the six competitions and nearly 20 years spanned by this project. This remains true for cruise, primary operations, and all of Phase E. Conclusions: A remarkable amount of science is accomplished by the science teams of planetary missions. However, a surprisingly small amount of funding is requested to support the science analysis driving this productivity, both in terms of absolute magnitude of funding and as a portion of total mission cost. This suggests improvements are needed to refine the estimates of Co-I support and/or that Co-Is rely on other funding sources to conduct their research. Better estimates can be determined by engaging directly with Co-Is and NASA centers to obtain data as well as finding other data sources. Additionally, NASA could consider mandating improved reporting of requested funding levels in mission competitions.

E Murray↗
DOE OSTI2012

In situ Characterization of Pt Catalysts Supported on Ceria Modified TiO(2) for the WGS reaction: Influence of Ceria Loading

This work analyzes the influence of cerium content (6-15 wt%) on a TiO{sub 2} support over the structure and water gas shift (WGS) activity of Pt catalysts. The structural properties of these Pt/Ce-TiO{sub 2} catalysts were characterized by XRD, TEM and XANES. Physicochemical characterization of the catalysts showed differences in the structure and dispersion of Ce entities on the support with Ce loading. For the samples with low ceria content (6 wt%), cerium is deposited on the support in the form of CeO{sub x} clusters in a highly dispersed state in close interaction with the Ti atoms. The formation of CeO{sub x} clusters at low Ce-loading on the support facilitates the dispersion of small particles of Pt and improves the reducibility of ceria component at low temperatures. The changes in platinum dispersion and support reducibility with Ce-loading on the TiO{sub 2} support lead to significant differences in the WGS activity. Pt supported on the sample with lower Ce content (6 wt%) shows better activity than those corresponding to catalysts with higher Ce content (15 wt%). Activity measurements coupled with catalysts characterization suggest that the improvement in the reducibility of the support with lower Ce content was associated with the presence of CeO{sub x} clusters of high reducibility that improve the chemical activity of the oxide-metal interfaces at which the WGS reaction takes place.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural cooling fluid tube for supporting a turbine component and supplying cooling fluid

A shaft cover support for a gas turbine engine is disclosed. The shaft cover support not only provides enhanced support to a shaft cover of the gas turbine engine, but also includes a cooling fluid chamber for passing fluids from a rotor air cooling supply conduit to an inner ring cooling manifold. As such, the shaft cover support accomplishes in a single component what was only partially accomplished in two components in conventional configurations. The shaft cover support may also provide additional stiffness and reduce interference of the flow from the compressor. In addition, the shaft cover support accommodates a transition section extending between compressor and turbine sections of the engine. The shaft cover support has a radially extending region that is offset from the inlet and outlet that enables the shaft cover support to surround the transition, thereby reducing the overall length of this section of the engine.

42 ENGINEERING↗
DOE OSTI2013

Supported PV module assembly

A supported PV assembly may include a PV module comprising a PV panel and PV module supports including module supports having a support surface supporting the module, a module registration member engaging the PV module to properly position the PV module on the module support, and a mounting element. In some embodiments the PV module registration members engage only the external surfaces of the PV modules at the corners. In some embodiments the assembly includes a wind deflector with ballast secured to a least one of the PV module supports and the wind deflector. An array of the assemblies can be secured to one another at their corners to prevent horizontal separation of the adjacent corners while permitting the PV modules to flex relative to one another so to permit the array of PV modules to follow a contour of the support surface.

42 ENGINEERING↗
DOE OSTI2013

Quantitative Z-Contrast Imaging of Supported Metal Complexes and Clusters - A Gateway to Understanding Catalysis on the Atomic Scale

Z-contrast imaging in an aberration-corrected scanning transmission electron microscope can be used to observe and quantify the sizes, shapes, and compositions of the metal frames in supported mono-, bi-, and multimetallic metal clusters and can even detect the metal atoms in single-metal-atom complexes, as well as providing direct structural information characterizing the metal-support interface. Herein, we assess the major experimental challenges associated with obtaining atomic resolution Z-contrast images of the materials that are highly beam-sensitive, that is, the clusters readily migrate and sinter on support surfaces, and the support itself can drastically change in structure if the experiment is not properly controlled. Calibrated and quantified Z-contrast images are used in conjunction with exsitu analytical measurements and larger-scale characterization methods such as extended X-ray absorption fine structure spectroscopy to generate an atomic-scale understanding of supported catalysts and their function. Examples of the application of these methods include the characterization of a wide range of sizes and compositions of supported clusters, primarily those incorporating Ir, Os, and Au, on highly crystalline supports (zeolites and MgO).

cluster compounds↗
DOE OSTI2020

Heterolytic Hydrogen Activation: Understanding Support Effects in Water–Gas Shift, Hydrodeoxygenation, and CO Oxidation Catalysis

Identifying the role of oxide supports in transition metal catalysis is critical toward our understanding of heterogeneous catalysis. The water-gas shift (WGS) reaction is a prototypical example where oxide support dictates catalytic activity, yet the cause for this remains uncertain. Herein, we show that a single descriptor—the equilibrium constant for hydroxyl formation—relates the WGS turnover frequency across disparate oxide supports. The dissimilar equilibrium constant, or oxophilicity, between early and late transition metals exemplify the utility of metal-support interfacial sites to circumvent adsorption-energy scaling restrictions, thereby providing bifunctional gains for the WGS reaction class. In relation, the equilibrium constant for hydroxyl formation is equivalent to the equilibrium constant for the formal heterolytic dissociation of hydrogen, and therefore, reflects the ability of the metal-support interface to participate in hydrogen heterolysis. The ubiquitous coexistence, yet divergent chemical behavior of homo- and heterolytically activated hydrogen renders oxide support identity central toward our understanding of hydrogenation catalysis. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences and performed at the Environmental Molecular Sciences Laboratory in (EMSL), which is a DOE Office of Science User Facility located at the Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. Computational resources were provided by a user proposal at the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility. N.N. would like to thank Oliver Y. Gutierrez for critical feedback during the final stage of manuscript preparation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Beating Heterogeneity of Single-Site Catalysts: MgO-Supported Iridium Complexes

Catalysts consisting of isolated metal atoms on oxide supports have attracted wide attention because they offer unique catalytic properties, but their structures remain largely unknown because the metals are bonded at various, heterogeneous surface sites. Now, by using highly crystalline MgO as a support for metal sites made from a mononuclear organoiridium precursor and investigating the surface species with X-ray absorption spectroscopy, atomic resolution electron microscopy, and electronic structure theory, we have differentiated among the MgO surface sites for iridium bonding. The results demonstrate the contrasting structures and catalytic properties of samples, even including those incorporating iridium at loadings as low as 0.01 wt % and showing that the latter are nearly ideal in the sense of having almost all the Ir atoms at equivalent surface sites, with each Ir atom bonded to three oxygen atoms of the MgO surface. These supported molecular catalysts are modeled accurately with density functional theory. The results open the door to the precise synthesis of families of single-site catalysts. The work was supported by the U.S. Department of Energy (DOE), Office of Science (SC), Basic Energy Sciences (BES), Grant DE-FG02-04ER15513 and the DOE BES Catalysis Center Program by a subcontract from Pacific Northwest National Laboratory (KC0301050-47319) to the University of Alabama. We thank Chevron for fellowship support of ASH and LMD. DAD thanks the Robert Ramsay Chair Fund of The University of Alabama for support. A portion of the research was performed using facilities of the Environmental Molecular Sciences Laboratory (Ringgold ID 130367), a DOE SC User Facility sponsored by the Office of Biological and Environmental Research. Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by DOE SC BES under Contract No. DE-AC02- 76SF00515. We thank Chevron Energy Technology Company for performing the XRD experiments.

single-site catalyst, iridium catalyst, MgO-suppor↗
DOE OSTI2016

A Sacrificial Coating Strategy Toward Enhancement of Metal-Support Interaction for Ultrastable Au Nanocatalysts

Supported gold (Au) nanocatalysts hold great promise for heterogeneous catalysis; however, their practical application is greatly hampered by poor thermodynamic stability. Herein, a general synthetic strategy is reported where discrete metal nanoparticles are made resistant to sintering, preserving their catalytic activities in high-temperature oxidation processes. Taking advantage of the unique coating chemistry of dopamine, sacrificial carbon layers are constructed on the material surface, stabilizing the supported catalyst. Upon annealing at high temperature under an inert atmosphere, the interactions between support and metal nanoparticle are dramatically enhanced, while the sacrificial carbon layers can be subsequently removed through oxidative calcination in air. Owing to the improved metal-support contact and strengthened electronic interactions, the resulting Au nanocatalysts are resistant to sintering and exhibit excellent durability for catalytic combustion of propylene at elevated temperatures. Moreover, the facile synthetic strategy can be extended to the stabilization of other supported catalysts on a broad range of supports, providing a general approach to enhancing the thermal stability and sintering resistance of supported nanocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Not all platinum surfaces are the same: Effect of the support on fundamental properties of platinum adlayer and its implications for the activity toward hydrogen evolution reaction

The adsorption of atomic hydrogen on a platinum monolayer supported on orthorhombic Mo 2 C(100) surface has been investigated, considering different hydrogen surface coverages. Calculations have been performed using density functional theory with the Perdew-Burke-Ernzerhof exchange correlation functional and a D3 Van der Waals corrections. The theoretical insight has been gained into atomic hydrogen interaction with Pt monolayer, supported on both molybdenum and well-studied tungsten carbide, and considering hydrogen surface coverage. Fundamental properties of Pt adlayer depend on the support, affecting hydrogen evolution activity of the resulting systems. At low hydrogen coverage all systems, with the exception of Pt supported on the molybdenum-terminated Mo 2 C, adsorb H comparably to a pristine Pt(111) surface and their high activity for the hydrogen evolution reaction is predicted. Additionally, at higher coverages supported Pt monolayers interact with atomic hydrogen unlike the Pt(111), suggesting that the activity of the supported and unsupported platinum toward hydrogen evolution reaction have different origins. Furthermore, the position of the supported platinum monolayers on the volcano curve is a function of the surface coverage, more so than for extended metal surfaces. Therefore, hydrogen surface coverage is a key variable to understand the catalytic potential, approaching towards an improved model for screening of electrocatalytic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tuning the Performance of Single-Atom Electrocatalysts: Support-Induced Structural Reconstruction

We present that creating active and stable electrocatalysts remains a highly desirable and critical goal in the fields of catalysis and clean energy conversion. Single-atom catalyst (SAC), as a new research frontier in heterogeneous catalysis, has demonstrated emerging prospects for many electrocatalytic reactions. Support assisted pyrolysis approaches are widely used in the synthesis of single-atom electrocatalysts. While extensive efforts have been devoted to increase the loading of the atomically dispersed metal sites, the role of the support in creating these active metal sites remains largely unexplored. Herein, we compare catalysts created by support-free and support-assisted pyrolysis of vitamin B12 and cobalt tetramethoxyphenylporphyrin, respectively, and demonstrate an important effect of support-induced structural reconstruction that directly controls the activation of SAC. Electrochemical studies show support-free catalysts are inactive for oxygen reduction reaction whereas the support-assisted pyrolysis yields highly active catalysts using the same molecular precursors. X-ray absorption spectroscopy experiments reveal that both the metal-nitrogen coordination and the type of nitrogen species are different in these two types of samples, which leads to a difference in the d-band of the cobalt metal center and ultimately controls the catalytic activity and stability. In conclusion, this new insight provides a unique perspective on how to tune the electrocatalytic performances of SAC at the molecular level.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

Room-Temperature Dynamics of Vanishing Copper Nanoparticles Supported on Silica

In heterogeneous catalysis, a nanoparticle (NP) system has immediate chemical surroundings with which its interaction needs to be considered, as nanoparticles are typically loaded onto certain supports. Beyond what is known about these interactions, dynamic atomic interactions between the nanoparticle and support could result from the increased energetics at the nanoscale. Here, we show that the dynamic response of atoms in copper nanoparticles to the underlying silica support at room temperature and ambient atmosphere results in the complete disappearance of supported nanoparticles over the course of only a few weeks. A quantitative study of copper nanoparticles at various size regimes (6-17 nm) revealed the significance of size-dependent nanoparticle energetics to the interaction with the support. Extended X-ray absorption fine structure is used to show that copper atoms could readily diffuse into the support to be locally surrounded by oxygen and silicon with structurally disordered outer coordination shells. Increased energetic states at the nanoscale and the energetically favorable configuration of individual copper atoms within silica, identified through EXAFS, are suggested as the cause of nanoparticle disappearance. This unexpected observation opens up new questions as to how nanoparticles interact with surrounding environments that could fundamentally change our conventional view of supported nanoparticle systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Supported Metal Pair-Site Catalysts

Complexes with neighboring metal centers in isolated pairs and their analogues on surfaces are drawing increasing attention as catalysts. These include molecular homogeneous catalysts incorporating various ligands, enzymes, and solids that include pairs of metal atoms mounted on supports. Catalysts in this broad class are active for numerous reactions and offer unexplored opportunities to address challenging reactions, such as oxidation of methane and oxidation of water in artificial photosynthesis. The subject of supported metal pair-site catalysts is in its infancy, facing challenges in (a) precise synthesis, (b) structure determination at the atomic scale, and (c) stabilization in reactive atmospheres. In this Perspective, we summarize key characteristics of molecular and enzymatic catalysts that incorporate neighboring metal centers and build on this foundation to assess the emerging literature of metal pair-site catalysts on various supports. The supported catalysts include those synthesized by anchoring molecular dinuclear precursors to support surfaces and those synthesized by selective formation of dinuclear surface species from mononuclear surface species. Examples of metals in this class are rhodium and iridium, and examples of supports are MgO and Fe 2 O 3 . We summarize characterization of these materials by electron microscopy and spectroscopy, emphasizing atomic-resolution aberration-corrected scanning transmission electron microscopy and spectroscopies that provide atomic-scale structural information and allow characterization of functioning catalysts, especially X-ray absorption spectroscopy. Finally, we list some opportunities for research, including suggestions that might lead to structurally well-defined supported metal pair-sites with new catalytic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electronic Structure of Atomically Dispersed Supported Iridium Catalyst Controls Iridium Aggregation

Supported iridium complexes, Ir(C 2 H 4 ) 2 /support, were characterized by X-ray absorption spectroscopy during a temperature ramp to 120 °C in flowing H 2 . Iridium in complexes bonded to weak and moderate electron-donor supports, SiO 2 and γ-Al 2 O 3 , underwent aggregation, forming nanoparticles and clusters, respectively. When the support was a strong electron-donor (MgO), iridium remained site-isolated. Density functional theory calculations confirm the dependence of iridium–support bond strength on the support’s electron-donor character. Coating the SiO 2 -supported complexes with 1-n-ethyl-3-methyl-imidazolium acetate enhanced electron density on the iridium, hindering its aggregation. Finally, these results demonstrate opportunities for stabilizing atomically dispersed supported noble metals under reducing conditions by choice of support/ionic liquid sheath combinations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗