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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 1,423 records · Page 79
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Hawaii Play Fairway Analysis: Lanai Resistivity and Density 3D Inversion Models

To prepare for its third phase, the Hawaii Play Fairway project conducted groundwater sampling and analyses in ten locations in the Hawaiian islands, magnetotelluric (MT) and gravity surveys, as well as calculations of 3D subsurface stress due to the weight of the rock underlying the topography of the volcano. The subsurface stresses were used to evaluate the potential for fracture-induced permeability. Inversions of the MT and gravity data produce 3D models of resistivity and density, respectively, on Lanai, across Haleakala's SW rift (Maui), and surrounding Mauna Kea (Hawaii Island). The project developed and applied a new method for incorporating depth information about resistivity, density, and potential for fracture-induced permeability into the statistical method for computing resource probability in these three focus areas. The project then incorporated the new groundwater results with the new geophysical results and the calculations of potential for fracture-induced permeability to produce updated maps of resource probability and confidence. These results were used to identify target sites for exploratory drilling. Spreadsheet information: Each sheet contains data for a particular depth in kilometers. Positive depths are above sea level, and negative below. For more information, go to the Hawaii Groundwater and Geothermal Resources Center website linked in the resources.

15 GEOTHERMAL ENERGY↗
DOE OSTI2021

Applying Waveform Correlation to Reduce Seismic Analyst Workload Due to Repeating Mining Blasts

Agencies that monitor for underground nuclear tests are interested in techniques that automatically characterize mining blasts to reduce the human analyst effort required to produce high–quality event bulletins. Waveform correlation is effective in finding similar waveforms from repeating seismic events, including mining blasts. We report the results of an experiment to detect and identify mining blasts for two regions, Wyoming (U.S.A.) and Scandinavia, using waveform templates recorded by multiple International Monitoring System stations of the Preparatory Commission for the Comprehensive Nuclear–Test–Ban Treaty Organization (CTBTO PrepCom) for up to 10 yr prior to the time of interest. We discuss approaches for template selection, threshold setting, and event detection that are specialized for characterizing mining blasts using a sparse, global network. We apply the approaches to one week of data for each of the two regions to evaluate the potential for establishing a set of standards for waveform correlation processing of mining blasts that can be generally applied to operational monitoring systems with a sparse network. Here, we compare candidate events detected with our processing methods to the Reviewed Event Bulletin of the International Data Centre to assess potential reduction in analyst workload.

58 GEOSCIENCES↗
DOE OSTI2023

URC Assessment Method

This tool evaluates the potential occurrence of URC resources using a series of validated heuristics as outlined in "Creason, C.G., Justman, D., Rose, K. et al. A Geo-Data Science Method for Assessing Unconventional Rare-Earth Element Resources in Sedimentary Systems. Nat Resour Res (2023). https://doi.org/10.1007/s11053-023-10163-x"

Critical Minerals↗
DOE OSTI2020

Developing and Evaluating Metrics for Demand Flexibility in Buildings: Comparing Simulations and Field Data

Building demand flexibility (DF) has attracted significant attention in recent years among researchers, technology developers and control companies, aggregators, utilities, and many others. There are numerous challenges with today’s electricity systems such as managing peak demand capacity and integrating variable renewables into the grid. Flexible building loads can provide various grid services to help reduce electricity costs, smooth out renewables intermittency and balance supply and demand. Recognizing this, the US DOE is leading the Grid-interactive Efficient Buildings (GEB) initiative which includes research to evaluate the potential, availability and timing of flexible loads. In this paper we present load shed metrics for three building types – medium office, large office and retail store – and compare prototype simulation results with measured data from 12 actual buildings that participated in hot summertime utility demand response (DR) events. The DR strategies included varying zone temperature and reducing light levels. The magnitude of a key DF metric, “demand decrease intensity” (or “shed intensity”) (W/ft2), between the simulation results and field data are similar (14-32% differences) for both mean and median values, though the field data show much larger variation among DR events. The coefficient p-values from linear regression model tests showed that outside air temperature is a significant variable for the whole building shed intensity when the resetting zone temperature strategy is deployed. These findings support the concept of using prototype building simulation to estimate building DF and expanding future simulation research to additional building types and climate zones.

Liu, Jingjing↗
DOE OSTI2018

Engineering Prediction of Axial Wellbore Shear Failure Caused by Reservoir Uplift and Subsidence

Injection and production can cause significant regional uplift or settlement. We analytically evaluate the potential for cement-annulus failure in response to injection-induced deformation in a coupled casing/cement/rock poromechanical vertical-well system. Deformation is calculated with respect to the initial near-wellbore stress state, occurring immediately after cement curing. Tensile-failure and shear-failure lengths along this well are predicted using a stress-development-length method. The analytical model is verified by Abaqus modeling. Lastly, a sensitivity analysis identifies critical engineering-well-design parameters for ensuring wellbore-annulus integrity.

58 GEOSCIENCES↗
DOE OSTI2019

Coupled Hydrodynamic-Geomechanical Modelling of CO2-WAG Field Development at Farnsworth Unit: A Case Study

Abstract The SWP project is located in a mature waterflood undergoing conversion to CO2-WAG operations at Farnsworth, Texas, USA. Utilized CO2 is anthropogenic, sourced from a fertilizer and an ethanol plant. Major project goals are optimizing the storage/production balance, ensuring storage permanence, and developing best practices for CCUS. This paper provides a review of work performed toward development of a 3D coupled Mechanical Earth Model (MEM) for use in assessment of caprock integrity, fault reactivation potential, and evaluation of stress dependent permeability in reservoir forecasting. Mechanical property estimates computed from geophysical logs at selected wellbores were integrated with 3D seismic elastic inversion products to create a 3D "static" mechanical property model sharing the same geological framework as the existing reservoir simulation model including 3 major faults. Stresses in the MEM were initialized from wellbore stress estimates and reservoir simulation pore pressures. One way and two way coupled simulations were performed using a compositional hydrodynamic flow model and geomechanical solvers. Coupled simulations were performed on history matched primary, secondary (waterflood), and tertiary (CO2 WAG) recovery periods, as well as an optimized WAG prediction period. These simulations suggest that the field has been operating at conditions which are not conducive to either caprock failure or fault reactivation. Two way coupled simulations were performed in which permeability was periodically updated as a function of volumetric strain using the Kozeny-Carmen porosity-permeability relationship. These simulations illustrate the importance of frequent permeability updating when recovery scenarios result in large pressure changes such as in field re-pressurization through waterflood after a long primary depletion recovery period. Conversely, production forecasting results are less sensitive to permeability update frequency when pressure cycles are short and shallow as in WAG cycles. This paper describes initial work on development of a mechanical earth model for use in assessment of geomechanical risks associated with CCUS operations at FWU. The emphasis of this work is on integration of available geomechanical data for creation of the static mechanical property model. Preliminary coupled hydro-mechanical simulations are presented to illustrate some of the key diagnostic output from coupled simulations which will be used in later work for in depth evaluation of specific risk factors such as induced seismicity and caprock integrity.

02 PETROLEUM↗
DOE OSTI2012

Geophysical Monitoring of Foam used to Deliver Remediation Treatments within the Vadose Zone

Foam is a promising vehicle for delivering amendments into the vadose zone for in situ remediation; it is an approach being considered for in situ treatment and stabilization of metals and radionuclides located within the deep vadose zone of the Department of Energy (DOE) Hanford site, WA. A central aspect of evaluating the effectiveness of this approach is the ability to monitor foam distribution, its transformation, and the reactions that it induces in the subsurface, ideally in a non-invasive manner. In this study, we performed laboratory experiments to evaluate the potential of geophysical methods (complex resistivity and time domain reflectometry, TDR) as tools for monitoring foam assisted amendment delivery in the deep vadose zone. Our results indicated great sensitivity of electrical methods to foam transportation and evolution in unsaturated porous media that were related to foam bubble coalescence and drainage processes. Specifically, we observed (1) a decrease of electrical resistivity (increase of electrical conductivity) by over an order of magnitude in both silica sand and natural sediment matrices during foam transportation; (2) an increase of resistivity (decrease of conductivity) by over two fold during foam coalescence and drainage; (3) a distinct phase and imaginary conductivity signature related to the evolution of water films on sediment grains during foam injection and evolution processes. To assist with the interpretation of these data, TDR measurements were used to monitor moisture content, which provided complementary information about foam distribution and drainage. Our results clearly demonstrated the sensitivity of electrical and TDR signals to foam transportation and evolution in unsaturated porous media and suggested the potential of these methods for monitoring the response of a system to foam based remediation treatments at field scales.

Hanford↗
DOE OSTI2012

Radar-Cross-Section Reduction of Wind Turbines (Part 1)

In recent years, increasing deployment of large wind-turbine farms has become an issue of growing concern for the radar community. The large radar cross section (RCS) presented by wind turbines interferes with radar operation, and the Doppler shift caused by blade rotation causes problems identifying and tracking moving targets. Each new wind-turbine farm installation must be carefully evaluated for potential disruption of radar operation for air defense, air traffic control, weather sensing, and other applications. Several approaches currently exist to minimize conflict between wind-turbine farms and radar installations, including procedural adjustments, radar upgrades, and proper choice of low-impact wind-farm sites, but each has problems with limited effectiveness or prohibitive cost. An alternative approach, heretofore not technically feasible, is to reduce the RCS of wind turbines to the extent that they can be installed near existing radar installations. This report summarizes efforts to reduce wind-turbine RCS, with a particular emphasis on the blades. The report begins with a survey of the wind-turbine RCS-reduction literature to establish a baseline for comparison. The following topics are then addressed: electromagnetic model development and validation, novel material development, integration into wind-turbine fabrication processes, integrated-absorber design, and wind-turbine RCS modeling. Related topics of interest, including alternative mitigation techniques (procedural, at-the-radar, etc.), an introduction to RCS and electromagnetic scattering, and RCS-reduction modeling techniques, can be found in a previous report.

17 WIND ENERGY↗
DOE OSTI2012

Methanogenic Conversion of CO 2 Into CH 4

This SBIR project evaluated the potential to remediate geologic CO 2 sequestration sites into useful methane gas fields by application of methanogenic bacteria. Such methanogens are present in a wide variety of natural environments, converting CO 2 into CH 4 under natural conditions. We conclude that the process is generally feasible to apply within many of the proposed CO 2 storage reservoir settings. However, extensive further basic R&D still is needed to define the precise species, environments, nutrient growth accelerants, and economics of the methanogenic process. Consequently, the study team does not recommend Phase III commercial application of the technology at this early phase.

03 NATURAL GAS↗
DOE OSTI2012

The effect of plutonium dioxide water surface coverage on the generation of hydrogen and oxygen

The conditions for the production of oxygen during radiolysis of water adsorbed onto plutonium dioxide powder are discussed. Studies in the literature investigating the radiolysis of water show that both oxygen and hydrogen can be generated from water adsorbed on high-purity plutonium dioxide powder. These studies indicate that there is a threshold in the amount of water below which oxygen is not generated. The threshold is associated with the number of monolayers of adsorbed water and is shown to occur at approximately two monolayers of molecularly adsorbed water. Material in equilibrium with 50% relative humidity (RH) will be at the threshold for oxygen generation. Using two monolayers of molecularly adsorbed water as the threshold for oxygen production, the total pressure under various conditions is calculated assuming stoichiometric production of hydrogen and oxygen. The specific surface area of the oxide has a strong effect on the final partial pressure. The specific surface areas resulting in the highest pressures within a 3013 container are evaluated. The potential for oxygen generation is mitigated by reduced relative humidity, and hence moisture adsorption, at the oxide surface which occurs if the oxide is warmer than the ambient air. The potential for oxygen generation approaches zero as the temperature difference between the ambient air and the material approaches 6°C.

08 HYDROGEN↗
DOE OSTI2012

Annual Report of Monitoring at Morrill, Kansas, in 2011

Carbon tetrachloride contamination in groundwater at Morrill, Kansas, was initially identified in 1985 during statewide testing of public water supply wells for volatile organic compounds (VOCs). High levels of nitrate were also present in the wells. The city of Morrill is located in Brown County in the northeastern corner of the state, about 7 mi east of Sabetha (Figure 1.1). The population of Morrill as of the 2010 Census was approximately 230 (down from 277 in 2000). All residents of Morrill now obtain their drinking water from the Sabetha municipal water system via a pipeline constructed in 1991. The findings of the April 2011 and October 2011 monitoring events at Morrill support the following conclusions: (1) Groundwater flow during the 2011 review period (as in prior years) was predominantly to the south, from the vicinity of the former CCC/USDA facility toward Terrapin Creek. Automatic water level monitoring data suggest that spring precipitation and recharge represent the predominant factors affecting the local groundwater level patterns. (2) No significant changes were observed in the concentration or distribution of carbon tetrachloride in groundwater during the spring and fall 2011 monitoring events versus the spring and fall 2010 monitoring events. In October 2011, a maximum carbon tetrachloride concentration of 49 μg/L was identified in groundwater at well MW3S on the former CCC/USDA facility, with concentrations decreasing downgradient toward Terrapin Creek. (3) Since 2004, the accumulated results of 15 sampling events have demonstrated a significant decline in the maximum detected concentration of carbon tetrachloride in groundwater. In 1995, the contaminant was detected at the former CCC/USDA facility at 390 μg/L, while the current maximum levels are < 50 μg/L. The residual contaminant plume extending from the former CCC/USDA facility southward toward Terrapin Creek is well-defined and slowly declining in concentration naturally. (4) No carbon tetrachloride contamination was detected in 2011 in surface waters or shallow streambed sediments sampled at five locations along Terrapin Creek, downgradient from the former CCC/USDA facility. These results indicate that Terrapin Creek remains unaffected by the carbon tetrachloride plume. (5) Since 2007, the accumulated results of 10 monitoring events for surface water and sediment in Terrapin Creek have demonstrated no impact to the sediment and surface waters of the creek by carbon tetrachloride and no imminent risk for further degradation of the creek. (6) Terrapin Creek (tributary segment 308 to Walnut Creek) receives discharge from the Morrill wastewater treatment plant and several confined animal feeding operations regulated by the KDHE. The Walnut Creek watershed is designated by the KDHE as impaired by fecal coliform bacteria. Terrapin Creek is classified by the KDHE as not open to or accessible by the public for contact recreation and does not support the food procurement designated use (KDHE 2010b). (7) In July 2011, trace concentrations of carbon tetrachloride were detected in vegetation samples collected from trees at 2 of the 42 sampled locations south (downgradient) of the former CCC/USDA facility. (8) Sampling of indoor air in August 2010 to evaluate the potential for vapor intrusion into homes overlying and within 100 ft laterally of the identified carbon tetrachloride plume resulted in no detections of carbon tetrachloride. Low concentrations of chloroform, indicative of indoor air sources, were detected. Low radon levels were also detected. The results indicate no evidence of upward migration of vapors from the low-level carbon tetrachloride contamination in groundwater to indoor air.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

A Preliminary Evaluation of Using Fill Materials to Stabilize Used Nuclear Fuel During Storage and Transportation

This report contains a preliminary evaluation of potential fill materials that could be used to fill void spaces in and around used nuclear fuel contained in dry storage canisters in order to stabilize the geometry and mechanical structure of the used nuclear fuel during extended storage and transportation after extended storage. Previous work is summarized, conceptual descriptions of how canisters might be filled were developed, and requirements for potential fill materials were developed. Elements of the requirements included criticality avoidance, heat transfer or thermodynamic properties, homogeneity and rheological properties, retrievability, material availability and cost, weight and radiation shielding, and operational considerations. Potential fill materials were grouped into 5 categories and their properties, advantages, disadvantages, and requirements for future testing were discussed. The categories were molten materials, which included molten metals and paraffin; particulates and beads; resins; foams; and grout. Based on this analysis, further development of fill materials to stabilize used nuclear fuel during storage and transportation is not recommended unless options such as showing that the fuel remains intact or canning of used nuclear fuel do not prove to be feasible.

Storage↗
DOE OSTI2012

Novel Approach to Prepare 99 mTc-Based Multivalent RGD Peptides

This project presents a novel approach to prepare the 99 mTc-bridged multivalent RGD (arginine-glycine-aspartate) peptides. This project will focus on fundamentals of 99 mTc radiochemistry. The main objective of this project is to demonstrate the proof-of-principle for the proposed radiotracers. Once a kit formulation is developed for preparation of the 9mTc-bridged multivalent RGD peptides, various tumor-bearing animal models will be used to evaluate their potential for SPECT (single photon-emission computed tomography) imaging of cancer.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

MPACT Fast Neutron Multiplicity System Design Concepts

This report documents work performed by Idaho National Laboratory and the University of Michigan in fiscal year (FY) 2012 to examine design parameters related to the use of fast-neutron multiplicity counting for assaying plutonium for materials protection, accountancy, and control purposes. This project seeks to develop a new type of neutron-measurement-based plutonium assay instrument suited for assaying advanced fuel cycle materials. Some current-concept advanced fuels contain high concentrations of plutonium; some of these concept fuels also contain other fissionable actinides besides plutonium. Because of these attributes the neutron emission rates of these new fuels may be much higher, and more difficult to interpret, than measurements made of plutonium-only materials. Fast neutron multiplicity analysis is one approach for assaying these advanced nuclear fuels. Studies have been performed to assess the conceptual performance capabilities of a fast-neutron multiplicity counter for assaying plutonium. Comparisons have been made to evaluate the potential improvements and benefits of fast-neutron multiplicity analyses versus traditional thermal-neutron counting systems. Fast-neutron instrumentation, using for example an array of liquid scintillators such as EJ-309, have the potential to either a) significantly reduce assay measurement times versus traditional approaches, for comparable measurement precision values, b) significantly improve assay precision values, for measurement durations comparable to current-generation technology, or c) moderating improve both measurement precision and measurement durations versus current-generation technology. Using the MCNPX-PoliMi Monte Carlo simulation code, studies have been performed to assess the doubles-detection efficiency for a variety of counter layouts of cylindrical liquid scintillator detector cells over one, two, and three rows. Ignoring other considerations, the best detector design is the one with the most detecting volume. However, operational limitations guide a) the maximum acceptable size of each detector cell (due to PSD performance and maximum-acceptable per-channel data throughput rates, limited by pulse pile-up and the processing rate of the electronics components of the system) and b) the affordability of a system due to the number of total channels of data to be collected and processed. As a first estimate, it appears that a system comprised of two rows of detectors 5" Ø $\times$ 3" would yield a working prototype system with excellent performance capabilities for assaying Pu-containing items and capable of handling high signal rates likely when measuring items with Pu and other actinides. However, it is still likely that gamma-ray shielding will be needed to reduce the total signal rate in the detectors. As a first step prior to working with these larger-sized detectors, it may be practical to perform scoping studies using small detectors, such as already-on-hand 3" Ø $\times$ 3" detectors.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2013

The Effect of Boron on the Thermal Sensitization of Grade ‘A’ Type 304 Stainless Steel

This technical work plan describes experimental work carried out at Los Alamos National Laboratory to evaluate the potential for thermal sensitization of Type 304 borated stainless steel, the leading candidate neutron absorber material for the permanent disposal of used nuclear fuel. This material may also be applicable for very long term storage, particularly if the canister is planned for direct disposal after storage. The workscope described here is new and seeks to provide information as to whether borated stainless steel would become sensitized with extended exposure to relatively high temperatures present in storage casks and disposal containers. This information is necessary to remove some of the conservatism contained in the corrosion allowances that have been applied to the Yucca Mountain Project waste packages, and are currently planned for the proposed can-in-can approach for direct disposal. Currently the corrosion allowance is a factor of nine above the measured corrosion rates for borated stainless steel in the relatively benign environments expected in a failed waste package, which is expected to be similar to dilute water in equilibrium with host rock.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

Tanks 18 And 19-F Structural Flowable Grout Fill Material Evaluation And Recommendations

Cementitious grout will be used to close Tanks 18-F and 19-F. The functions of the grout are to: 1) physically stabilize the final landfill by filling the empty volume in the tanks with a non-compressible material; 2) provide a barrier for inadvertent intrusion into the tank; 3) reduce contaminant mobility by a) limiting the hydraulic conductivity of the closed tank and b) reducing contact between the residual waste and infiltrating water; and 4) providing an alkaline, chemically reducing environment in the closed tank to control speciation and solubility of selected radionuclides. The objective of this work was to identify a single (all-in-one) grout to stabilize and isolate the residual radionuclides in the tank, provide structural stability of the closed tank and serve as an inadvertent intruder barrier. This work was requested by V. A. Chander, High Level Waste (HLW) Tank Engineering, in HLW-TTR-2011-008. The complete task scope is provided in the Task Technical and QA Plan, SRNL-RP-2011-00587 Revision 0. The specific objectives of this task were to: 1) Identify new admixtures and dosages for formulating a zero bleed flowable tank fill material selected by HLW Tank Closure Project personnel based on earlier tank fill studies performed in 2007. The chemical admixtures used for adjusting the flow properties needed to be updated because the original admixture products are no longer available. Also, the sources of cement and fly ash have changed, and Portland cements currently available contain up to 5 wt. % limestone (calcium carbonate). 2) Prepare and evaluate the placement, compressive strength, and thermal properties of the selected formulation with new admixture dosages. 3) Identify opportunities for improving the mix selected by HLW Closure Project personnel and prepare and evaluate two potentially improved zero bleed flowable fill design concepts; one based on the reactor fill grout and the other based on a shrinkage compensating flowable fill mix design. 4) Prepare samples for hydraulic property measurements for comparison to the values in the F- and H- Tank Farm Performance Assessments (PAs). 5) Identify a grout mix for the Tanks 18-F and 19-F Grout Procurement Specification. Results for two flowable zero bleed structural fill concepts containing 3/8 inch gravel (70070 Series and LP#8 Series) and a sand only mix (SO Series) are provided in this report. Tank Farm Engineering and SRNL Project Management selected the 70070 mix as the base case for inclusion in Revision 0 of the Tanks 18-F and 19-F grout procurement specification and requested admixture recommendations and property confirmation for this formulation. Lower cementitious paste mixes were formulated because the 70070 mix is over designed with respect to strength and generates more heat from hydration reactions than is desirable for mass pour application. Work was also initiated on a modification of the recommended mix which included shrinkage compensation to mitigate fast pathways caused by shrinkage cracking and poor physical bonding to the tank and ancillary equipment. Testing of this option was postponed to FY12. Mix, LP#8-16 is recommended for inclusion in the specification for furnishing and delivering tank closure grout for Tanks 18-F and 19-F. A shrinkage compensating variation of this mix, LP#16C, has not been fully developed and characterized at this time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Membrane Process to Capture CO 2 from Coal-Fired Power Plant Flue Gas

This final report describes work conducted for the U.S. Department of Energy National Energy Technology Laboratory (DOE NETL) on development of an efficient membrane process to capture carbon dioxide (CO 2 ) from power plant flue gas (award number DE-NT0005312). The primary goal of this research program was to demonstrate, in a field test, the ability of a membrane process to capture up to 90% of CO 2 in coal-fired flue gas, and to evaluate the potential of a full-scale version of the process to perform this separation with less than a 35% increase in the levelized cost of electricity (LCOE). Membrane Technology and Research (MTR) conducted this project in collaboration with Arizona Public Services (APS), who hosted a membrane field test at their Cholla coal-fired power plant, and the Electric Power Research Institute (EPRI) and WorleyParsons (WP), who performed a comparative cost analysis of the proposed membrane CO 2 capture process.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2013

High-Spin Cobalt Hydrides for Catalysis

Organometallic chemists have traditionally used catalysts with strong-field ligands that give low-spin complexes. However, complexes with a weak ligand field have weaker bonds and lower barriers to geometric changes, suggesting that they may lead to more rapid catalytic reactions. Developing our understanding of high-spin complexes requires the use of a broader range of spectroscopic techniques, but has the promise of changing the mechanism and/or selectivity of known catalytic reactions. These changes may enable the more efficient utilization of chemical resources. A special advantage of cobalt and iron catalysts is that the metals are more abundant and cheaper than those currently used for major industrial processes that convert unsaturated organic molecules and biofeedstocks into useful chemicals. This project specifically evaluated the potential of high-spin cobalt complexes for small-molecule reactions for bond rearrangement and cleavage reactions relevant to hydrocarbon transformations. We have learned that many of these reactions proceed through crossing to different spin states: for example, high-spin complexes can flip one electron spin to access a lower-energy reaction pathway for beta-hydride elimination. This reaction enables new, selective olefin isomerization catalysis. The high-spin cobalt complexes also cleave the C-O bond of CO2 and the C-F bonds of fluoroarenes. In each case, the detailed mechanism of the reaction has been determined. Importantly, we have discovered that the cobalt catalysts described here give distinctive selectivities that are better than known catalysts. These selectivities come from a synergy between supporting ligand design and electronic control of the spin-state crossing in the reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗