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At least 469 records · Page 26

Stellar and Binary Evolution in Star Clusters

This paper presents a final report on research activities covered on Stellar and Binary Evolution in Star Clusters. Substantial progress was made in the development and dissemination of the "Starlab" software environment. Significant improvements were made to "kira," an N-body simulation program tailored to the study of dense stellar systems such as star clusters and galactic nuclei. Key advances include (1) the inclusion of stellar and binary evolution in a self-consistent manner, (2) proper treatment of the anisotropic Galactic tidal field, (3) numerous technical enhancements in the treatment of binary dynamics and interactions, and (4) full support for the special-purpose GRAPE-4 hardware, boosting the program's performance by a factor of 10-100 over the accelerated version. The data-reduction and analysis tools in Starlab were also substantially expanded. A Starlab Web site (http://www.sns.ias.edu/-starlab) was created and developed. The site contains detailed information on the structure and function of the various tools that comprise the package, as well as download information, "how to" tips and examples of common operations, demonstration programs, animations, etc. All versions of the software are freely distributed to all interested users, along with detailed installation instructions.

McMillan, Stephen L. W.↗

A second generation experiment in fault-tolerant software

Information was collected on the efficacy of fault-tolerant software by conducting two large-scale controlled experiments. In the first, an empirical study of multi-version software (MVS) was conducted. The second experiment is an empirical evaluation of self testing as a method of error detection (STED). The purpose ot the MVS experiment was to obtain empirical measurement of the performance of multi-version systems. Twenty versions of a program were prepared at four different sites under reasonably realistic development conditions from the same specifications. The purpose of the STED experiment was to obtain empirical measurements of the performance of assertions in error detection. Eight versions of a program were modified to include assertions at two different sites under controlled conditions. The overall structure of the testing environment for the MVS experiment and its status are described. Work to date in the STED experiment is also presented.

Knight, J. C.↗

Mars Lander/Rover vehicle development: An advanced space design project for USRA and NASA/OAST

The results of the studies on one particular part of the Mars Lander/Rover (MLR) system are contained: the Balloon Rover. This component vehicle was selected for further research and design because of the lack of technical literature on this subject, as compared to surface rover technology. Landing site selection; balloon system development and deployment; optics and communications; and the payload power supply are described.

Source record↗

A dendritic strontium river isoscape for fisheries applications in the Sacramento River basin, California, USA

Objective Understanding the origins and movements of fish is fundamental to effective conservation and fisheries management. Strontium isotope ratios ( 87 Sr/ 86 Sr) in otoliths provide a powerful tracer of natal origin and migratory pathways. However, existing 87 Sr/ 86 Sr isoscapes for the Sacramento River basin, an ecosystem that supports ecologically and economically important salmon populations, rely on discrete classification approaches that overlook unsampled habitats and do not incorporate spatial uncertainty. Our objective was to develop a continuous, network-explicit 87 Sr/ 86 Sr isoscape with quantified uncertainty to fill in data gaps and enable probabilistic assignments of fish origin and movement. Methods We used river water 87 Sr/ 86 Sr data from 106 sites (1997–2021) to develop spatial stream network models that use dendritic connectivity and watershed characteristics (lithology, bedrock age, and land cover) to predict river water 87 Sr/ 86 Sr throughout the basin. Models were fitted using maximum and restricted likelihood and were evaluated via Akaike’s information criterion and leave-one-out cross validation. We produced both historical (pre-dam) and present-day (below-dam) isoscapes, delineated uncertainty-informed isotopic ranges using k -means clustering, and applied a proof-of-concept Bayesian assignment to estimate natal origins and early rearing habitats for two endangered winter-run Chinook Salmon Oncorhynchus tshawytscha. Results Cross validation indicated strong performance of the 87 Sr/ 86 Sr model (leave-one-out cross validation: R 2 = 0.91; root mean square error = 0.0005). Uncertainty-informed clustering identified 19 isotopic “suites” (reaches with indistinguishable 87 Sr/ 86 Sr values) in present-day anadromous habitats and 25 suites in the historical network. Example natal and early rearing assignments included predictions that challenged expectations for juvenile salmon migration based on predicted river 87 Sr/ 86 Sr compositions. Conclusions This study developed a continuous, network-explicit 87 Sr/ 86 Sr isoscape that integrates existing river data to predict 87 Sr/ 86 Sr in unsampled reaches and the likely achievable range and resolution of otolith-based origin and life history inference. The resulting river isoscape provides a valuable tool to predict salmon movements and identify habitats supporting their survival and growth that otherwise might remain undetected. Coupling these predictions with complementary approaches that ground-truth juvenile presence (e.g., targeted fish surveys) represents an important step toward science-informed restoration and management of critical habitats throughout the Sacramento River basin.

Environmental sciences↗

Human and Robotic Exploration Missions to Phobos Prior to Crewed Mars Surface Missions

Phobos is a scientifically significant destination that would facilitate the development and operation of the human Mars transportation infrastructure, unmanned cargo delivery systems and other Mars surface systems. In addition to developing systems relevant to Mars surface missions, Phobos offers engineering, operational, and public engagement opportunities that could enhance subsequent Mars surface operations. These opportunities include the use of low latency teleoperations to control Mars surface assets associated with exploration science, human landing‐site selection and infrastructure development which may include in situ resource utilization (ISRU) to provide liquid oxygen for the Mars Ascent Vehicle (MAV). A human mission to Mars' moons would be preceded by a cargo predeploy of a surface habitat and a pressurized excursion vehicle (PEV) to Mars orbit. Once in Mars orbit, the habitat and PEV would spiral to Phobos using solar electric propulsion based systems, with the habitat descending to the surface and the PEV remaining in orbit. When a crewed mission is launched to Phobos, it would include the remaining systems to support the crew during the Earth‐Mars transit and to reach Phobos after insertion in to Mars orbit. The crew would taxi from Mars orbit to Phobos to join with the predeployed systems in a spacecraft that is based on a MAV, dock with and transfer to the PEV in Phobos orbit, and descend in the PEV to the surface habitat. A static Phobos surface habitat was chosen as a baseline architecture, in combination with the PEV that was used to descend from orbit as the main exploration vehicle. The habitat would, however, have limited capability to relocate on the surface to shorten excursion distances required by the PEV during exploration and to provide rescue capability should the PEV become disabled. To supplement exploration capabilities of the PEV, the surface habitat would utilize deployable EVA support structures that allow astronauts to work from portable foot restraints or body restrain tethers in the vicinity of the habitat. Prototype structures were tested as part of NEEMO 20. PEVs would contain closed loop guidance and provide life support and consumables for two crew for 2 weeks plus reserves. The PEV has a cabin that uses the exploration atmosphere of 8.2 psi with 34% oxygen, enabling use of suit ports for rapid EVA with minimal oxygen prebreathe as well as dust control by keeping the suits outside the pressurized volume. When equipped with outriggers and control moment gyros, the PEV enables EVA tasks of up to 8 pounds of force application without the need to anchor. Tasks with higher force requirements can be performed with PEV propulsion providing the necessary thrust to react forces. Exploration of Phobos builds heavily from the developments of the cis‐lunar proving ground, and significantly reduces Mars surface risk by facilitating the development and testing of habitats, MAVs, and pressurized rover cabins that are all Mars surface forward. A robotic precursor mission to Phobos and Deimos is also under consideration and would need to launch in 2022 to support a 2031 human Phobos mission.

Gernhardt, Michael L.↗

Human and Robotic Exploration Missions to Phobos Prior to Crewed Mars Surface Missions

Phobos is a scientifically significant destination that would facilitate the development and operation of the human Mars transportation infrastructure, unmanned cargo delivery systems and other Mars surface systems. In addition to developing systems relevant to Mars surface missions, Phobos offers engineering, operational, and public engagement opportunities that could enhance subsequent Mars surface operations. These opportunities include the use of low latency teleoperations to control Mars surface assets associated with exploration science, human landing-site selection and infrastructure development, which may include in situ resource utilization (ISRU) to provide liquid oxygen for the Mars Ascent Vehicle (MAV). A human mission to Mars' moons would be preceded by a cargo pre-deploy of a surface habitat and a pressurized excursion vehicle (PEV) to Mars orbit. Once in Mars orbit, the habitat and PEV would spiral to Phobos using solar electric propulsion based systems, with the habitat descending to the surface and the PEV remaining in orbit. When a crewed mission is launched to Phobos, it would include the remaining systems to support the crew during the Earth-Mars transit and to reach Phobos after insertion in to Mars orbit. The crew would taxi from Mars orbit to Phobos to join with the predeployed systems in a spacecraft that is based on a MAV, dock with and transfer to the PEV in Phobos orbit, and descend in the PEV to the surface habitat. A static Phobos surface habitat was chosen as a baseline architecture, in combination with the PEV that was used to descend from orbit as the main exploration vehicle. The habitat would, however, have limited capability to relocate on the surface to shorten excursion distances required by the PEV during exploration and to provide rescue capability should the PEV become disabled. To supplement exploration capabilities of the PEV, the surface habitat would utilize deployable EVA support structures that allow astronauts to work from portable foot restraints or body restrain tethers in the vicinity of the habitat. Prototype structures were tested as part of NEEMO 20.

Gernhardt, Michael L.↗

Site-specific Design Case Study for Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels

Hydrothermal liquefaction (HTL) is a thermal process that converts wet biomass to renewable hydrocarbon fuel blendstocks (i.e., renewable naphtha, renewable diesel, and sustainable aviation fuel (SAF)). It can utilize a wide range of pure and blended wet feedstocks, including sewage sludge from water resource recovery facilities (WRRF), food and agriculture wastes, algae, fats, oils and greases (FOG) and blends of dry and wet wastes/feedstocks. Historically, techno-economic analysis (TEA) and annual state of technology (SOT) assessments with standard economic assumptions used by the Bioenergy Technologies Office (BETO) were conducted for the wet waste HTL pathway leveraging experimental data collected from Pacific Northwest National Laboratory’s (PNNL) continuous flow reactor systems. The objective of the SOT assessment has been to guide and track progress of BETO’s HTL research and development (R&D) toward reduced cost and greenhouse gas (GHG) emissions for the pathway. However, gaps exist between BETO’s traditional SOT updates and the needs of key external stakeholders that – if addressed – will accelerate technology adoption. This Business Case Study aims to bridge this gap by providing an updated design, TEA, and LCA based on PNNL’s FY23 R&D with added analyses and information that provide enhanced relevance for stakeholders of the HTL technology. This includes specific siting, regional wet waste resource inventory and transportation cost analyses, fuel market information, sustainable fuel policy impacts, economic metrics of net present value (NPV) and internal rate of return (IRR), greenhouse gas (GHG) emissions analysis, and statistical analysis of cost and technical uncertainties of the HTL plant design. The study focuses on the “Detroit combined statistical area (CSA)” region for siting of a wet waste HTL plant adjacent to the Great Lakes Water Authority (GLWA) facility with guidance from industry participants. Regional resource and siting analyses were conducted to identify feedstock availability, scale, and cost, as well as a beneficial site location. TEA with detailed rigorous capital cost estimation for the specific site application was conducted to evaluate the key economic metrics of most value to industrial partners. These include total capital investment, operating costs, minimum fuel selling price (MFSP) of the biocrude and fuel blendstock, and NPV and internal rate of return IRR with sustainable fuel credits. Life cycle analysis was conducted to evaluate the supply chain greenhouse gas (GHG) emissions for the wet waste HTL process as compared with petroleum derived diesel. This study is also informed by years of R&D and process de-risking learnings and was conducted with a basic engineering HTL plant design and costing that akin to a “first-of-a-kind” plant economics. This differs from our conventional “nth plant ” SOT assessments. Specifically, the HTL process model has been updated with more operationally reliable methods for feed heating and phase separations. Further, we have implemented additional spare equipment for redundancy, a more rigorous installed equipment cost estimation approach, and additional costs associated with feed formatting and delivery, building, piping and site development. An Excel-based cost sheet based on the basic engineering design is also released alongside the report that allows users to conduct customized TEA with their own feed composition and financial assumptions.

09 BIOMASS FUELS↗

Supporting data for Site-specific Design Case Study for Wet Waste Hydrothermal Liquefaction and Biocrude Upgrading to Hydrocarbon Fuels

Hydrothermal liquefaction (HTL) is a thermal process that converts wet biomass to renewable hydrocarbon fuel blendstocks (i.e., renewable naphtha, renewable diesel, and sustainable aviation fuel (SAF)). It can utilize a wide range of pure and blended wet feedstocks, including sewage sludge from water resource recovery facilities (WRRF), food and agriculture wastes, algae, fats, oils and greases (FOG) and blends of dry and wet wastes/feedstocks. Historically, techno-economic analysis (TEA) and annual state of technology (SOT) assessments with standard economic assumptions used by the Bioenergy Technologies Office (BETO) were conducted for the wet waste HTL pathway leveraging experimental data collected from Pacific Northwest National Laboratory’s (PNNL) continuous flow reactor systems. The objective of the SOT assessment has been to guide and track progress of BETO’s HTL research and development (R&D) toward reduced cost and greenhouse gas (GHG) emissions for the pathway. However, gaps exist between BETO’s traditional SOT updates and the needs of key external stakeholders that – if addressed – will accelerate technology adoption. This Business Case Study aims to bridge this gap by providing an updated design, TEA, and LCA based on PNNL’s FY23 R&D with added analyses and information that provide enhanced relevance for stakeholders of the HTL technology. This includes specific siting, regional wet waste resource inventory and transportation cost analyses, fuel market information, sustainable fuel policy impacts, economic metrics of net present value (NPV) and internal rate of return (IRR), greenhouse gas (GHG) emissions analysis, and statistical analysis of cost and technical uncertainties of the HTL plant design. The study focuses on the “Detroit combined statistical area (CSA)” region for siting of a wet waste HTL plant adjacent to the Great Lakes Water Authority (GLWA) facility with guidance from industry participants. Regional resource and siting analyses were conducted to identify feedstock availability, scale, and cost, as well as a beneficial site location. TEA with detailed rigorous capital cost estimation for the specific site application was conducted to evaluate the key economic metrics of most value to industrial partners. These include total capital investment, operating costs, minimum fuel selling price (MFSP) of the biocrude and fuel blendstock, and NPV and internal rate of return IRR with sustainable fuel credits. Life cycle analysis was conducted to evaluate the supply chain greenhouse gas (GHG) emissions for the wet waste HTL process as compared with petroleum derived diesel. This study is also informed by years of R&D and process de-risking learnings and was conducted with a basic engineering HTL plant design and costing that akin to a “first-of-a-kind” plant economics. This differs from our conventional “nth plant ” SOT assessments. Specifically, the HTL process model has been updated with more operationally reliable methods for feed heating and phase separations. Further, we have implemented additional spare equipment for redundancy, a more rigorous installed equipment cost estimation approach, and additional costs associated with feed formatting and delivery, building, piping and site development. An Excel-based cost sheet based on the basic engineering design is also released alongside the report that allows users to conduct customized TEA with their own feed composition and financial assumptions.

Li, Shuyun↗

Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High‐Efficient Atomically Dispersed CoN 4 Active Sites

Abstract We elucidate the structural evolution of CoN 4 sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)‐8‐derived carbon host as an ideal model for Co 2+ ion adsorption. Subsequent in situ X‐ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co−OH and Co−O species into active CoN 4 sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four‐electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal‐induced compressive strain of Co−N bonds in CoN 4 active sites formed at 900 °C. Further, we developed a two‐step (i.e., Co ion doping and adsorption) Co‐N‐C catalyst with increased CoN 4 site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

He, Yanghua↗

Risk to Ecological Resources on Burial Waste Sites on the Hanford Site, Washington - 20248

The US and other nations have a large nuclear and chemical waste remediation task remaining from World War II, the Cold War, and industrial activities. The US Department of Energy (DOE) has the largest task in the U.S., with Hanford (Washington State) being the most contaminated site, with the longest and most costly cleanup program projected to extend to the end of the century. One of the greatest remediation problems at Hanford are the burial waste facilities, some of which are inside the 200 Areas on the Central Plateau, while others are outside the 200 Areas. These areas are associated with waste sites, pipes, and contaminated trenches, posing technical cleanup challenges to meet DoE's remediation goals, including protection of human health and the environment commensurate with Tri- Party Agreement and current regulatory requirements. In this paper we select one of the legacy waste sites (the BC Cribs and Trenches) as a case study to explore how risk to ecological resources varies during and as a consequence of remediation on sites primarily considered legacy waste sites. We used the risk methodology developed by the Consortium for Risk Evaluation with Stakeholder Participation (CRESP) during the Hanford Site-wide Risk Review. The CRESP methodology included evaluating the risk to receptors, including human health, the Columbia River, groundwater, and ecological and cultural resources. The risk evaluation process for ecological receptors included defining the boundaries of each evaluation unit (EU) to be remediated, definition of a suitable buffer area that might be affected, and consideration of the known resource value based on field work. This information, coupled with known remediation options or strategies, allowed us to develop a risk rating for ecological resources. Site risks were evaluated on a scale of 'not discernible' to 'very high' risk. Consideration of the risks at the buried waste sites was complicated by uncertainties in remediation methods and the degree of restoration that would occur as part of the remediation process. We use the BC Cribs and Trenches as a case study to explore why the risks are low currently but increase during remediation. The current 'not discernible to low' risk rating is due to the lack of high quality ecological resources on the BC Cribs and Trenches EU, except for edge areas (with some state-listed species). During remediation the risks increase to 'medium', mainly due to high quality resources on adjacent buffer lands, which could be disrupted during active remediation. Medium and high quality resources on the edge of the site are continuous with higher quality native shrub-steppe habitat on the buffer. Ecological resources on some of the areas surrounding the 200 East and West Areas are some of the highest quality shrub-steppe areas on the Hanford Site, and risk to these resources could be prevented by planning before and during remediation to minimize disruption. For example, lay down areas for the BC Cribs and Trenches can be minimized by careful planning. Heavy truck and other vehicular traffic can be minimized. Spread of the noxious weeds now on some of the site can be prevented, and the spread of invasive species into the site (particularly near undisturbed shrub-steppe habitat) can be reduced. Further, the areas around and between the 200 East and West Areas have been largely undisturbed and can serve as a source of seeds and propagules for any revegetation that occurs as part of the remediation process. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

1999 Marsokhod Field Experiment: A Simulation of a Mars Rover Science Mission

A field experiment to simulate a rover mission to Mars was performed in February 1999. This experiment, the latest in a series of rover field experiments, was designed to demonstrate and validate technologies and investigation strategies for high-science, high-technology performance, and cost-effective planetary rover operations. Objectives: The experiment objectives were to: (1) train scientists in a mission configuration relevant to Surveyor program rover missions at a terrestrial analog field site simulating the criteria of high-priority candidate landing-sites on Mars; (2) develop optimal exploration strategies; (3) evaluate the effectiveness of imaging and spectroscopy in addressing science objectives; (4) assess the value and limitation of descent imaging in supporting rover operations; and (5) evaluate the ability of a science team to correctly interpret the geology of the field site using rover observations. A field site in the California Mojave Desert was chosen for its relevance to the criteria for landing site selection for the Mars Surveyor program. These criteria are: (1) evidence of past water activity; (2) presence of a mechanism to concentrate life; (3) presence of thermal energy sources; (4) evidence of rapid burial; and (5) excavation mechanisms that could expose traces of life.

Stoker, C.↗

EGIS - An Environmental GIS Developed for NASA Field Center Applications

As the principal center for Environmental Geographic Information Systems (EGIS), the John C. Stennis Space Center (SSC), located in Hancock County, Mississippi, has been assigned technical support requirements to design and to implement a basic EGIS data base for all NASA Field Centers. The intent of this Phase I effort is to produce a baseline EGIS data base incorporating newly available remotely sensed data as well as existing environmental data. A example application of the use of the data base at Stennis Space Center will be to illustrate baseline environmental conditions for consideration with proposed propulsion test stand development and operation. To effectively answer questions related to environmental issues at each center, organization of the data layers and sources will include the following categories: Cadastral/Geodetic; Geopolitical; Hydrography; Infrastructure; Physical Geography; Socioeconomic; Remote Sensing Imagery; Associated Metadata. As part of a Phase II effort, site-specific data and applications will be implemented and added to the data base at each Field Center. This poster illustrates the framework of the design and implementation of a basic EGIS data base. Shown are example data sources, hardware and software, and data base delivery and installation. The poster also depicts future recommendations for a centrally located server to house each of the NASA Field Center data bases. The server will allow real-time data base updates with additional layers and models for each center. Expansion of the EGIS data base will continue to grow as site-specific applications are developed addressing the ongoing evolution of environmental concerns at all NASA Field Centers.

Smoot, James↗

Status Quo and Gap Analysis of Heliostat Field Deployment Processes for Concentrating Solar Tower Plants

In this study, deployment of the solar field of a concentrating solar power plant is one of many factors that are integral to the success of a project. Knowledge transfer from outside the industry is limited due to the unique nature of heliostats, which redirect sunlight to a receiver with high precision while maintaining a high level of reflectivity. Moreover, learning from project to project can be limited due to the site-specific nature of projects, as the market includes several developers, each with their own unique design. In this paper, we discuss the state of the art in heliostat field deployment. We cover all the key aspects of deployment from project assessment to a fully functioning system, which include site selection, layout development, supply chain, assembly, site preparation and construction, calibration, and operations and maintenance. We then perform a gap analysis on field deployment and recommend priorities for future research.

14 SOLAR ENERGY↗

Atomically Precise Single-Site Catalysts via Exsolution in a Polyoxometalate–Metal–Organic-Framework Architecture

Single-site catalysts (SSCs) achieve a high catalytic performance through atomically dispersed active sites. A challenge facing the development of SSCs is aggregation of active catalytic species. Reducing the loading of these sites to very low levels is a common strategy to mitigate aggregation and sintering; however, this limits the tools that can be used to characterize the SSCs. Here we report a sintering-resistant SSC with high loading that is achieved by incorporating Anderson–Evans polyoxometalate clusters (POMs, MMo 6 O 24 , M = Rh/Pt) within NU-1000, a Zr-based metal–organic framework (MOF). The dual confinement provided by isolating the active site within the POM, then isolating the POMs within the MOF, facilitates the formation of isolated noble metal sites with low coordination numbers via exsolution from the POM during activation. The high loading (up to 3.2 wt %) that can be achieved without sintering allowed the local structure transformation in the POM cluster and the surrounding MOF to be evaluated using in situ X-ray scattering with pair distribution function (PDF) analysis. Notably, the Rh/Pt···Mo distance in the active catalyst is shorter than the M···M bond lengths in the respective bulk metals. Furthermore, models of the active cluster structure were identified based on the PDF data with complementary computation and X-ray absorption spectroscopy analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Web Time-Management Tool

Oak Grove Reactor, developed by Oak Grove Systems, is a new software program that allows users to integrate workflow processes. It can be used with portable communication devices. The software can join e-mail, calendar/scheduling and legacy applications into one interactive system via the web. Priority tasks and due dates are organized and highlighted to keep the user up to date with developments. Reactor works with existing software and few new skills are needed to use it. Using a web browser, a user can can work on something while other users can work on the same procedure or view its status while it is being worked on at another site. The software was developed by the Jet Propulsion Lab and originally put to use at Johnson Space Center.

Source record↗

Clock synchronization experiments using OMEGA transmissions

The OMEGA transmissions from North Dakota on 13.10 and 12.85 kHz were monitored at several sites using a recently developed OMEGA timing receiver specifically designed for this purpose. The experiments were conducted at Goddard Space Flight Center, Greenbelt, Maryland; U.S. Naval Observatory, Washington, D.C.; and at the NASA tracking station, Rosman, North Carolina. Results show that cycle identification of the two carrier frequencies was made at each test site, thus, coarse time (76 microseconds) from the OMEGA transmitted signals to within the ambiguity period of each OMEGA frequency was extracted. The fine time determination, which was extracted from the phase difference between the received OMEGA signals and locally generated signals, was about + or - 2 microseconds for daytime reception and about + or - 5 microseconds for nighttime reception.

Chi, A. R.↗

Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High-Efficient Atomically Dispersed CoN 4 Active Sites

We elucidate the structural evolution of CoN 4 sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)-8-derived carbon host as an ideal model for Co 2+ ion adsorption. Subsequent in situ X-ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co-OH and Co-O species into active CoN 4 sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four-electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal-induced compressive strain of Co-N bonds in CoN 4 active sites formed at 900 °C. Further, we developed a two-step (i.e., Co ion doping and adsorption) Co-N-C catalyst with increased CoN 4 site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Triplet Resonating Valence Bond State and Superconductivity in Hund’s Metals

A central idea in strongly correlated systems is that doping a Mott insulator leads to a superconductor by transforming the resonating valence bonds (RVBs) into spin-singlet Cooper pairs. Here, we argue that a spin-triplet RVB (tRVB) state, driven by spatially, or orbitally anisotropic ferromagnetic interactions can provide the parent state for triplet superconductivity. We apply this idea to the iron-based superconductors, arguing that strong on site Hund’s interactions develop intra-atomic tRVBs between the $t_{2_g}$ orbitals. On doping, the presence of two iron atoms per unit cell allows these interorbital triplets to coherently delocalize onto the Fermi surface, forming a fully gapped triplet superconductor. In this work, this mechanism gives rise to a unique staggered structure of on site pair correlations, detectable as an alternating π phase shift in a scanning Josephson tunneling microscope.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗