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DOE OSTI2024

Production of Bioproducts from Electrochemically-Generated C1 Intermediates

The overarching objective of the project was to develop an integrated process that converts carbon dioxide (CO 2 ) into the platform chemical isopropanol (IPA) using a combination of two key technologies: CO 2 electrolysis and gas fermentation. The final goal was to demonstrate the full process at bench scale with a minimum carbon conversion efficiency of 37% and to evaluate the economics and environmental impact of scaling up the electrochemical-biochemical process.

30 DIRECT ENERGY CONVERSION↗

NASA NTRS1977

The Missions of the Viking Orbiters

A description of the orbiter science instruments is presented and the chronology of the two Viking missions is reviewed. The design of the Viking orbiter spacecraft is discussed, taking into account the propulsion subsystem, the attitude control subsystem, the planetary scan platform, aspects of command processing, problems of instrument operation and data processing, and data quantity limitations. Details concerning the Viking orbits and the visibility of the planet are also considered and the future of the Viking orbiter missions is evaluated. If the orbiters continue to perform well, all the orbiter science investigations will continue to acquire data for another year and perhaps somewhat longer.

Snyder, C. W.↗

NASA NTRS1979

A telescopic jib for continuous adjustment

For special space applications, e.g. for experiments distant from any orbital platforms or manipulators a new kind of jibs with extreme extension capacity has to be designed. Considering the requirements, the telescopic principle is found to be the most promising. For the choice of the stiff structure, design criteria are evaluated. Special effort deals with the drive system. An electromechanical system can satisfy the requirements. First results of the development of such a drive are presented. The most significant features are: A telescopic assembly of tubes which can be mutually moved by a short spindle in the center of the package. An elastically suspended screw is located at the bottom of each tube. For the jib extension, these screws will be linked with the spindle. The control of their sequence and the adjustment of tubes in mutual end positions are performed by latches. A functional model proved the basic idea.

Etzler, C. C.↗

NASA NTRS1990

Deep-space radiation exposure analysis for solar cycle XXI (1975-1986)

Ionizing radiation exposures and associated dosimetric quantities are evaluated for the 11-year solar cycle ending in 1986. Solar flare fluences for the 55 largest flares occurring during the cycle are superimposed on the Galactic cosmic ray flux. Published summaries of flare data from the Interplanetary Monitoring Platform (IMP)-7 and IMP-8 satellites are used that include flares whose integrated fluences are greater than 10 to the 7th protons/sq cm for energies in excess of 10 MeV. A standard cosmic ray environment model for ion flux values at solar minimum and maximum is invoked with an assumed sinusoidal variation between the lower and upper limits. The radiation shielding analysis is carried out for equivalent water-shield thicknesses between 2 and 15 g/sq cm. Results are expressed in terms of cumulative incurred dose equivalents for deep-space missions lasting between 3 months and 3 years. It was found that medium-to-large flare contributions are of greatest importance for the shorter term missions, while the Galactic component dominates for the longer duration missions.

Nealy, John E.↗

NASA NTRS2002

Incompressible Navier-Stokes Solvers in Primative Variables and their Applications to Steady and Unsteady Flow Simulations

This paper reviews recent progress made in incompressible Navier-Stokes simulation procedures and their application to problems of engineering interest. Discussions are focused on the methods designed for complex geometry applications in three dimensions, and thus are limited to primitive variable formulation. A summary of efforts in flow solver development is given followed by numerical studies of a few example problems of current interest. Both steady and unsteady solution algorithms and their salient features are discussed. Solvers discussed here are based on a structured-grid approach using either a finite -difference or a finite-volume frame work. As a grand-challenge application of these solvers, an unsteady turbopump flow simulation procedure has been developed which utilizes high performance computing platforms. In the paper, the progress toward the complete simulation capability of the turbo-pump for a liquid rocket engine is reported. The Space Shuttle Main Engine (SSME) turbo-pump is used as a test case for evaluation of two parallel computing algorithms that have been implemented in the INS3D code. The relative motion of the grid systems for the rotorstator interaction was obtained using overact grid techniques. Unsteady computations for the SSME turbo-pump, which contains 114 zones with 34.5 million grid points, are carried out on SCSI Origin 3000 systems at NASA Ames Research Center. The same procedure has been extended to the development of NASA-DeBakey Ventricular Assist Device (VAD) that is based on an axial blood pump. Computational, and clinical analysis of this device are presented.

Kiris, Cetin C.↗

NASA NTRS2016

Development of a Heterogeneous sUAS High-Accuracy Positional Flight Data Acquisition System

Recently, a heterogeneous FDAS, consisting of a diverse range of instruments was developed to support acoustic flight research programs at NASA Langley Research Center. In addition to a conventional GPS to measure latitude, longitude and altitude, the FDAS also utilizes a small, light-weight, low-cost DGPS system to obtain centimeter accuracy to measure the distance traveled by sound from a sUAS vehicle to a microphone on the ground. Acoustic flight testing using the FDAS installed on several different sUAS platforms has been conducted in support of the NASA CAS DELIVER and ERA ITD projects (Reference 1). The first FDAS prototype was assembled and implemented in the acoustic/flight measurement system in December 2014 to support DELIVER acoustic flight tests. Evaluation of the system performance and results from the data analyses were used to further test, develop and enhance the FDAS over a six-month period to support acoustic flight research for the ERA.

McSwain, Robert G.↗

NASA NTRS2018

Required Time of Arrival as a Control Mechanism to Mitigate Uncertainty in Arrival Traffic Demand Management

The objective of this study is to explore the use of Required Time of Arrival (RTA) capability on the flight deck as a control mechanism on arrival traffic management to improve traffic delivery accuracy by mitigating the effect of traffic demand uncertainty. The uncertainties are caused by various factors, such as departure error due to the difference between scheduled departure and the actual take-off time. A simulation study was conducted using the Multi Aircraft Control System (MACS) software, a comprehensive research platform developed in the Airspace Operations Laboratory (AOL) at NASA Ames Research Center. The Crossing Time (CT) performance (i.e. the difference between target crossing time and actual crossing time) of the RTA for uncertainty mitigation during cruise phase was evaluated under the influence of varying two main factors: wind severity (heavy wind vs. mild wind), and wind error (1 hour, 2 hours, and 5 hours wind forecast errors). To examine the CT performance improvement made by the RTA, the comparison to the CT of the aircraft that were not assigned with RTA (Non-RTA) under the influence of the selected factors was also made. The Newark Liberty International Airport (EWR) was chosen for this study. A total 66 inbound traffic to the EWR (34 of them were airborne when the simulation was initiated, 32 were pre-departures at that time) was simulated, where the pre-scripted departure error was assigned to each pre-departure (61 conform to their Expected Departure Clearance Time, which is +-300 seconds of their scheduled departure time). The results of the study show that the delivery accuracy improvement can be achieved by assigning RTA, regardless of the influence of the selected two factors (the wind severity and the wind information inaccuracy). Across all wind variances, 66.9 (265 out of 396) of the CT performance of the RTA assigned aircraft was within +- 60 seconds (i.e. target tolerance range) and 88.9 (352 out of 396) aircraft met +-300 seconds marginal tolerance range, while only 33.6 (133 out of 396) of the Non-RTA assigned aircrafts CT performance achieved the target tolerance range and 75.5 (299 out of 396) stayed within the marginal. Examination of the impact of different error sources i.e. departure error, wind severity, and wind error suggest that although large departure errors can significantly impact the CT performance, the impacts of wind severity and errors were modest relative the targeted +- 60 second conformance range.

required time of arrival (RTA)↗

NASA NTRS2020

Reducing Errors in Velocity–Azimuth Display (VAD) Wind and Deformation Retrievals from Airborne Doppler Radars in Convective Environments

The present study describes methods to reduce the uncertainty of velocity–azimuth display (VAD) wind and deformation retrievals from downward-pointing, conically scanning, airborne Doppler radars. These retrievals have important applications in data assimilation and real-time data processing. Several error sources for VAD retrievals are considered here, including violations to the underlying wind field assumptions, Doppler velocity noise, data gaps, temporal variability, and the spatial weighting function of the VAD retrieval. Specific to airborne VAD retrievals, we also consider errors produced due to the radar scans occurring while the instrument platform is in motion. While VAD retrievals are typically performed using data from a single antenna revolution, other strategies for selecting data can be used to reduce retrieval errors. Four such data selection strategies for airborne VAD retrievals are evaluated here with respect to their effects on the errors. These methods are evaluated using the second hurricane nature run numerical simulation, analytic wind fields, and observed Doppler radar radial velocities. The proposed methods are shown to reduce the median absolute error of the VAD wind retrievals, especially in the vicinity of deep convection embedded in stratiform precipitation. The median absolute error due to wind field assumption violations for the along-track and for the across-track wind is reduced from 0.36 to 0.08 m s−1 and from 0.35 to 0.24 m s−1, respectively. Although the study focuses on Doppler radars, the results are equally applicable to conically scanning Doppler lidars as well.

Charles N Helms↗

DOE OSTI2017

A SUMMARY COMPARISON OF DESIGN EVALUATION TECHNIQUES

The United States’ fleet of Nuclear Reactors is considering modernizing their control rooms and instrumentation as an effort to avoid component obsolescence, keep up with competing industries, and cater to a new work force among others. Multiple technologies have potential to improve the control room. In attempts to evaluate the available options researchers employ a variety of measures to ensure the best candidate is used in a modernizing effort. The NRC is in charge of ensuring any new design has been thoroughly vetted before approving a license. Laid out in NUREG-0711 “Human Factors Engineering Program Review Model” is the review criteria for design validation. As there are a variety of measures currently used to evaluate candidate technologies, this paper seeks to identify weaknesses in the common measures used to design and validate technology in control room modernization efforts. Identifying where measurements are not meeting the criteria will help the control room modernization research platform identify where measurement development needs to occur. This will help ensure that current performance measurements are producing as reliable results as possible to select the right technology to integrate into nuclear operating control rooms.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2020

Computationally Aided Design of a Small-Scale Waste-Glass Melter - 20452

To provide mission support to the WTP for the vitrification of legacy nuclear tank waste at the Hanford site, a reduced-scale vitrification pilot system is being designed to process simulated and actual radioactive tank wastes. The waste stored in underground tanks will be separated into HLW and LAW fractions, where the majority is LAW by mass (approximately 90%) and HLW by activity (greater than 95%). The first tank waste to be processed at the WTP will be LAW. Because Hanford tank waste and the resultant melter feed compositions are known to vary widely, pilot-scale operations are essential to identify potential problems, provide needed data, confirm assumptions, and determine impacts to full-scale melters and off-gas systems from these different feeds. In addition, the reduced-scale melter system must be capable of quickly providing results to operations without the typically high cost of full-scale radioactive operations and to provide an engineering platform in close proximity to local operations staff. The objectives of this computational modeling effort are to produce process conditions like those encountered in the WTP LAW melters and to minimize the volume of radioactive waste necessary for the evaluations. To this end, melter design features are being explored to increase production without significantly increasing surface area or melter-glass volumes or compromising data quality. In support of these objectives, a set of computational fluid dynamic models was developed to provide insight into the flow patterns within these small melters and evaluate design features to increase production without significantly increasing glass inventory. Computed velocities were evaluated at the interface between the cold cap and the molten-glass pool and within the bulk-glass pool. Since melt rate correlates with the velocity underneath the cold cap, this information can be used to select design features that produce the highest gains. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Evaluation of a land-atmosphere coupling metric computed from a ground-based infrared interferometer

Land-atmosphere feedbacks are a critical component of the hydrologic cycle. Vertical profiles of boundary layer temperature and moisture, together with information about the land surface, are used to compute land-atmosphere coupling metrics. Ground based remote sensing platforms, such as the Atmospheric Emitted Radiance Interferometer (AERI), can provide high temporal resolution vertical profiles of temperature and moisture. When co-located with soil moisture, surface flux, and surface meteorological observations, such as at the Atmospheric Radiation Measurement (ARM) Southern Great Plains (SGP) site, it is possible to observe both the terrestrial and atmospheric legs of land-atmosphere feedbacks. In this study, we compare a commonly used coupling metric computed from radiosonde-based data to that obtained from the AERI to characterize the accuracy and uncertainty in the metric derived from the two distinct platforms. This approach demonstrates the AERI’s utility where radiosonde observations are absent in time and/or space. Radiosonde and AERI based observations of the Convective Triggering Potential and Low-Level Humidity Index (CTP-HI low ) were computed during the 1200 UTC observation time and displayed good agreement during both 2017 and 2019 warm seasons. Furthermore, radiosonde and AERI derived metrics diagnosed the same atmospheric preconditioning based upon the CTP-HI low framework a majority of the time. When retrieval uncertainty was considered, even greater agreement was found between radiosonde and AERI derived classification. The AERI’s ability to represent this coupling metric well enabled novel exploration of temporal variability within the overnight period in CTP and HI low . Observations of CTP-HI low computed within a few hours of 1200 UTC were essentially equivalent, however with greater differences in time arose greater differences in CTP and HI low .

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2003

Preliminary Design, Feasibility and Cost Evaluation of 1- to 15-Kilometer Height Steel Towers

Design and construction of tall towers is an on-going research program of NASA. The agency has already done preliminary review in this area and has determined that multi-kilometer height towers are technically and economically feasible. The proposed towers will provide high altitude launch platforms reaching above eighty percent of Earth's atmosphere and provide tremendous gains in the potential energy as well as substantial reduction in aerodynamic drag. NASA has also determined that a 15-KM tower will have many useful applications in: (i)Meteorology,(ii)Oceanography, (iii)Astronomy, (iv)High Altitude Launch, (v)Physics Drop Tower, (vi) Biosphere Research, (vii) Nanotechnology, (viii) Energy/Power, (ix)Broadband Wireless Technology, (x)Space Transportation and (xi)Space Tourism.

Shanker, Ajay↗

NASA NTRSDate not supplied

Exposure of Highly Reflective Far-Ultraviolet Coatings to LEO Environment for TRL Advancement for the Habitable Worlds Observatory

Over the past several years, our team at the NASA Goddard Space Flight Center (GSFC), in collaboration with the Jet Propulsion Laboratory (JPL) and the Naval Research Laboratory (NRL), have developed several new protected Al coating technologies with improved Far-Ultraviolet (FUV) reflectance performance and more robust environmental stability. These include Al protected with lithium-based fluoride (LiF) coatings such as hot deposited LiF (eLiF), XeF 2 -passivated LiF coatings (XeLiF), Li 3 AlF 6 overcoats, AlF 3 (plasma passivated), and XeF 2 passivated MgF 2 coatings (XeMgF 2 ). However, despite these developments, relatively little experimental information exists regarding the long-term stability of these coatings after simultaneous exposure to the Low Earth Orbit (LEO) environment. To evaluate their environmental durability and advance their Technology Readiness Level (TRL), representative samples of these coating technologies, Al+XeLiF, Al+eLiF, Al+Li 3 AlF 6 , Al+AlF 3 , Al+XeMgF 2 , and bare Al as reference samples, were flown onboard the International Space Station (ISS) as part of the Materials International Space Station Experiment 20 (MISSE-20). The MISSE platform is operated by Aegis Aerospace for relatively long-duration (e.g. 6 months) external exposure experiments in a space environment. The coatings were deposited on ULE and Zerodur substrates, and witness samples deposited on the same coatings runs, but on glass slides were left on Earth as control. A subset of the flight samples were fitted with MgF 2 windows to reduce direct exposure to atomic oxygen (AO) and charged particles, and still let through UV and other types of radiation on these samples. After approximately 6 months of exposure in the forward-facing (RAM) direction, the samples were returned to Earth and characterized by performing FUV/NUV/VIS/NIR reflectance measurements to quantify degradation, spectroscopic ellipsometry to evaluate coating thickness and optical constants, atomic force microscopy (AFM) to quantify surface roughness evolution during the flight in the ISS. The MgF 2 protective windows were also analyzed through FUV transmission measurements. Comparison with the witness samples left on the ground and with the flown bare Al samples (with just the naturally occurring Al 2 O 3 layer) provided a quantitative assessment of coating thickness variations, optical performance degradation, and morphological changes induced by prolonged exposure to the LEO environment.

Far Ultraviolet (FUV)↗

DOE OSTI2023

Risk Analysis of Various Design Architectures for High Safety-significant Safety-related Digital Instrumentation and Control Systems of Nuclear Power Plants during Accident Scenarios

This report documents the plus-up activities performed by Idaho National Laboratory (INL) during Fiscal Year (FY) 2022 for the U.S. Department of Energy (DOE) Light Water Reactor Sustainability (LWRS) Program, Risk Informed Systems Analysis (RISA) Pathway, digital instrumentation and control (DI&C) risk assessment project. In FY 2019, the RISA Pathway initiated a project to develop a risk assessment strategy for delivering a strong technical basis to support effective, licensable, and secure DI&C technologies for digital upgrades/designs. An integrated risk assessment technology for the DI&C systems was proposed for this strategy, which aims to (1) provide a best-estimate, risk-informed capability to quantitatively and accurately estimate the safety margin obtained from plant modernization, especially for the high safety-significant safety-related (HSSSR) DI&C systems, (2) support and supplement existing advanced risk-informed DI&C design guides by providing quantitative risk information and evidence, (3) offer a capability of design architecture evaluation of various DI&C systems to support system design decisions and diversity and redundancy applications, (4) assure the long-term safety and reliability of HSSSR DI&C systems, and (5) reduce uncertainty in costs and support integration of DI&C systems in the plant. To achieve these technical goals and deal with the expensive licensing justifications from regulatory insights, the LWRS-developed framework instructs nuclear vendors and utilities on how to effectively lower the costs associated with digital compliance and speed industry advances by: (1) defining an integrated risk-informed analysis process for DI&C upgrade, including hazard analysis, reliability analysis, and consequence analysis, (2) applying systematic and risk-informed tools to address common cause failures (CCFs) and quantify corresponding failure probabilities for DI&C technologies, particularly software CCFs, (3) evaluating the impact of digital failures at the component level, system level, and plant level, and (4) providing insights and suggestions on designs to manage the risks, thus to support the development, licensing, and deployment of advanced DI&C technologies on nuclear power plant (NPPs). Adding diversity within system or components is the main means to eliminate and mitigate CCFs, but diversity also increases plant complexity and errors and may not address all sources of systematic failures. How to optimize the diversity and redundancy applications for the safety-critical DI&C systems remains a challenge. To deal with the technical issues in addressing potential software CCFs in HSSSR DI&C systems of NPPs and supporting relevant design optimization, the framework provides: ? An integrated best-estimate, risk-informed capability to address new technical digital issues quantitatively, accurately, and efficiently in plan modernization progress, such as software CCFs in HSSSR DI&C systems of NPPs ? A common and a modularized platform for DI&C designers, software developers, cybersecurity analysts, and plant engineers to efficiently predict and prevent risk in the early design stage of DI&C systems ? Technical bases and risk-informed insights to assist U.S. Nuclear Regulatory Commission (NRC) and industry to address and fulfill the risk-informed alternatives for evaluation of CCFs in HSSSR DI&C systems of NPPs ? An integrated risk-informed tool that offers a capability of design architecture evaluation of various DI&C systems to support system design decisions in diversity and redundancy applications. The plus-up research and development efforts of this project in FY 2022 are focused on methodology improvement of software CCF modeling and estimation, prevention analysis, importance analysis and risk analysis of various design architectures of HSSSR DI&C systems. This work greatly enhances the capability of the LWRS-developed framework for the risk assessment and design optimization of safety-critical DI&C systems. It should be noted that all the analyses are performed for the demonstration of the LWRS-developed framework, not for the evaluation of relevant systems. Results are obtained based on very limited design information and testing data.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2016

Comparison of proton therapy treatment planning for head tumors with a pencil beam algorithm on dual and single energy CT images

Purpose: Dual energy CT (DECT) has recently been proposed as an improvement over single energy CT (SECT) for stopping power ratio (SPR) estimation for proton therapy treatment planning (TP), thereby potentially reducing range uncertainties. Published literature investigated phantoms. This study aims at performing proton therapy TP on SECT and DECT head images of the same patients and at evaluating whether the reported improved DECT SPR accuracy translates into clinically relevant range shifts in clinical head treatment scenarios. Methods: Two phantoms were scanned at a last generation dual source DECT scanner at 90 and 150 kVp with Sn filtration. The first phantom (Gammex phantom) was used to calibrate the scanner in terms of SPR while the second served as evaluation (CIRS phantom). DECT images of five head trauma patients were used as surrogate cancer patient images for TP of proton therapy. Pencil beam algorithm based TP was performed on SECT and DECT images and the dose distributions corresponding to the optimized proton plans were calculated using a Monte Carlo (MC) simulation platform using the same patient geometry for both plans obtained from conversion of the 150 kVp images. Range shifts between the MC dose distributions from SECT and DECT plans were assessed using 2D range maps. Results: SPR root mean square errors (RMSEs) for the inserts of the Gammex phantom were 1.9%, 1.8%, and 1.2% for SECT phantom calibration (SECT{sub phantom}), SECT stoichiometric calibration (SECT{sub stoichiometric}), and DECT calibration, respectively. For the CIRS phantom, these were 3.6%, 1.6%, and 1.0%. When investigating patient anatomy, group median range differences of up to −1.4% were observed for head cases when comparing SECT{sub stoichiometric} with DECT. For this calibration the 25th and 75th percentiles varied from −2% to 0% across the five patients. The group median was found to be limited to 0.5% when using SECT{sub phantom} and the 25th and 75th percentiles varied from −1% to 2%. Conclusions: Proton therapy TP using a pencil beam algorithm and DECT images was performed for the first time. Given that the DECT accuracy as evaluated by two phantoms was 1.2% and 1.0% RMSE, it is questionable whether the range differences reported here are significant.

61 RADIATION PROTECTION AND DOSIMETRY↗

NASA NTRS1994

SPICE: An innovative, flexible instrument concept

Studies and plans for orbital capture of cosmic dust and interplanetary dust particles (IDP's) looked very bright with the advent of space station Freedom (SSF) and formal selection of Cosmic Dust Collection Facility (CDCF) as an attached payload in 1990. Unfortunately it has been downhill since its selection, culminating in CDCF being dropped as attached payload in the SSF redesign process this year. This action was without any input from the science or cosmic dust communities. The Exobiology Intact Capture Experiment (Exo-ICE) as an experiment on CDCF was also lost. Without CDCF, no facility-class instrument for cosmic dust studies is available or planned. When CDCF (and Exo-ICE) was selected as a SSF attached payload, an exercise called the small particle intact capture experiment (SPICE) was started for Exo-ICE to develop an understanding and early testing of the necessary expertise and technology for intact capture of cosmic dust and IDP's. This SPICE activity looks to fly small, meter square or less, collection area experiments on early orbital platforms of opportunity such as EURECA, MIR, WESTAR, and others, including the shuttle. The SPICE activity has focused on developing techniques and instrument concepts to capture particles intact and without inadvertent contamination. It began with a survey and screening of available capture media concepts and then focused on the development of a capture medium that can meet these requirements. Evaluation and development of the chosen capture medium, aerogel (a silicon oxide gel), has so far lived up to the expectations of meeting the requirements and is highlighted in a companion paper at this workshop. Others such as McDonnell's Timeband Capture Cell Experiment (TICCE) on EuReCa and Tsuo's GAS-CAN lid experiments on STS 47 and 57 have flown aerogel, but without addressing the contamination issue/requirement, especially regarding organics. Horz, Zolenskym and others have studied and have also been advocates for its development. The SPICE instrument's experiment design builds on the knowledge gained from these efforts to meet the intact capture, noncontamination requirements. An overview of a possible SPICE experimental instrument concept using the MIR space station as a host platform for cosmic dust collection is provided in this paper. The SPICE concept is nonplatform-specified and can fly on any platform that provides a mode for experiment recovery.

Nishioka, Kenji↗

DOE OSTI2016

A knowledge brokerage approach for assessing the impacts of the setting up young farmers policy measure in Greece

This study explores Knowledge Brokerage (KB) aspects of an ex-post Impact Assessment (IA) for the Rural Development Programme (RDP) measure of setting up young farmers, under the Common Agricultural Policy (CAP), at the regional level in Northern Greece. The measure supports the entry of young farmers in agriculture by moving land from older to younger farmers. The aim of the study was to test a set of KB tools for improving the interaction between researchers and policy makers. Our analysis mainly focused on a suite of IA Support Modules to guide practitioners, and on a technical tool kit, a web-based contextualisation platform, to support the IA of the specific test case. Offering a structured approach towards IA, both the Support Modules and LIAISE-KIT allow framing the context, organisation, scheduling and method selection in the light of KB objectives. The evaluation of how IA Support Modules influence the Science Policy Interface (SPI), in the case of the ex-post assessment, demonstrated the high relevance of KB activities for facilitating the interaction between researchers and regional policy makers. The assessment bridges the gap between knowledge producers developing scientific output to be applied in a specific context, and knowledge users, who want clear messages regarding the policy challenges they face. Other conclusions include the need for specific guidelines and training for knowledge users, especially with regard to the use of tools. According to our findings, a consequent application of KB activities is a crucial pre-condition for successfully implementing IAs in future RDP measures.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex That Efficiently Promotes the 4e – /4H + Peractivation of O 2 to Water

The selective 4e – /4H + reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) or Co(III) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. Furthermore, these systems have been repeatedly shown to be selective for O 2 reduction by the less desired 2e – /2H + pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based on a nonaromatic isocorrole scaffold that is competent for 4e – /4H + oxygen reduction reaction (ORR). This Co(II) 10,10-dimethyl isocorrole (Co[10-DMIC]) is obtained in just four simple steps and has excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co porphyrin (cobalt 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, [Co(TPFPP)]) and corrole (cobalt 5,10,15-tris(pentafluorophenyl)corrole triphenylphosphine, Co[TPFPC](PPh 3 )) homologues demonstrated that the spectroscopic and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, the investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e – /4H + reduction of O 2 to H 2 O over the more kinetically facile 2e – /2H + process that delivers H 2 O 2 . In contrast, the same ORR evaluations conducted for the Co porphyrin and corrole homologues demonstrated that these traditional aromatic systems catalyze the 2e – /2H + conversion of O 2 to H 2 O 2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups or ditopic molecular clefts or that impose cofacially oriented O 2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and shows a privileged performance for the 4e – /4H + peractivation of O 2 to water as compared to other simple cobalt containing tetrapyrroles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗