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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Integrated operation scenarios: Chapter 6 of the special issue: on the path to tokamak burning plasma operation

Here we report the progress of the development and optimization of operational scenarios for ITER and beyond, focusing upon baseline, hybrid, and steady-state scenarios since 2007. This includes advancements made by the integrated operation scenarios (IOS) topical group of the international tokamak physical activity as well as contributions from the broader tokamak community. The key area of research involves developing IOSs that encompass tokamak physics, operation, and technology by utilizing integrated modeling and control strategies. This requires leveraging available actuators to simultaneously control plasma position and shape, MHD activities that could lead to disruptions, transport, plasma-wall interaction and power exhaust, fuel cycle, fusion burn, and tritium breeding. The control extends from the plasma initiation phase, through the current ramp-up, flattop, start and end of the fusion burn, and current ramp-down, to the plasma termination phase. A review of the currently developed scenarios and modeling is provided in terms of (i) optimizing plasma initiation in ITER, (ii) preparing for the low activation phase to fully commission all tokamak systems and establish and validate physics and scenario conditions in preparation for deuterim-tritium (DT) operation, (iii) developing and preparing baseline and hybrid scenarios to demonstrate the feasibility of achieving these regimes within device constraints, (iv) exploring steady-state scenarios to meet ITER’s steady-state goals, (v) evaluating and preparing actuators for ITER, (vi) developing integrated control solutions using shared actuators. The most notable achievements include; (i) the development of ITER demonstration discharges by matching various dimensionless parameters, (ii) the development of scenarios in an ITER-like tungsten environment and DT operation, and (iii) the development of scenarios in superconducting tokamaks, enabling long-pulse operations with similar coil constraints to ITER. Along with these significant achievements, outstanding issues and recommendations for further research and development are provided. Importantly, this study goes beyond simply updating the ITER Physics Basis; it carries profound implications for the broader field of burning plasma research, offering valuable insights and guidance for the next generation of fusion experiments and devices.

ITER↗
DOE OSTI2025

Temporal Galactose‐Manganese Feeding in Fed‐Batch and Perfusion Bioreactors Modulates UDP‐Galactose Pools for Enhanced mAb Glycosylation Homogeneity

ABSTRACT Monoclonal antibodies (mAbs) represent a majority of biotherapeutics in the market today. These glycoproteins undergo posttranslational modifications, such as N‐linked glycosylation, that influence the structural & functional characteristics of the antibody. Glycosylation is a heterogenous posttranslational modification that may influence therapeutic glycoprotein stability and clinical efficacy, which is why it is often considered a critical quality attribute (CQA) of the mAb product. While much is known about the glycosylation pathways of Chinese Hamster Ovary (CHO) cells and how cell culture chemical modifiers may influence the N‐glycosylation profile of the final product, this knowledge is often based on the final cumulative glycan profile at the end of the batch process. Building a temporal understanding of N‐glycosylation and how mAb glycoform composition responds to real‐time changes in the biomanufacturing process will help build integrated process models that may allow for glycosylation control to produce a more homogenous product. Here, we look at the effect of specific nutrient feed media additives (e.g., galactose, manganese) and feeding times on the N‐glycosylation pathway to modulate N‐glycosylation of a Herceptin biosimilar mAb (i.e., Trastuzumab). We deploy the N‐GLYcanyzer process analytical technology (PAT) to monitor glycoforms in near real‐time for bench‐scale bioprocesses operated in both fed‐batch and perfusion modes to build an understanding of how temporal changes in mAb N‐glycosylation are dependent on specific media additives. We find that Trastuzumab terminal galactosylation is sensitive to media feeding times and intracellular nucleotide sugar pools. Temporal analysis reveals an increased desirable production of single and double galactose‐occupied glycoforms over time under glucose‐starved fed‐batch cultures. Comparable galactosylation profiles were also observed between fed‐batch (nutrient‐limited) and perfusion (non‐nutrient‐limited) bioprocess conditions. In summary, our results demonstrate the utility of real‐time monitoring of mAb glycoforms and feeding critical cell culture nutrients under fed‐batch and perfusion bioprocessing conditions to produce higher‐quality biologics.

Biotechnology & Applied Microbiology↗
DOE OSTI2025

Advanced defrosting techniques in air source heat pumps: A review of vapor injection, thermal energy storage, and experimental frost accumulation data

Electrification is a critical step for reducing greenhouse gas emissions from heating. Air source heat pumps (ASHPs) are a promising alternative to fossil fuel-based systems due to their high coefficients of performance (COP), dual heating and cooling capability, and lower carbon footprint. However, for ASHPs to achieve widespread adoption, they must operate reliably across all climates, including cold regions. Additionally, defrosting techniques should be energy efficient and minimally disruptive to indoor comfort. Vapor injection (VI) technology can address the high-pressure and high-temperature lift challenges encountered in low ambient conditions. More recently, in addition to enhancing heating performance, VI has also been shown to improve the speed and efficiency of reverse cycle defrosting. Likewise, thermal energy storage (TES) has steadily gained attention for its ability to serve as an auxiliary heat source during both normal operation and defrosting. This review analyzes the benefits and limitations of VI- and TES-assisted defrosting approaches. While both technologies show strong potential individually, no studies to date have explored their combined use in ASHP systems. Additionally, to support continued development of defrosting strategies, both in modeling and experimental work, it is critical to establish frost accumulation data under a range of operating conditions. By compiling the available data from the literature, this paper also highlights the limited availability of such experimental data and the wide variation in frosting and defrosting durations and termination criteria, which are often influenced by system design and test setups.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

A data-driven operational model for traffic at the Dallas Fort Worth International Airport

Airports are on the front line of significant innovations, allowing the movement of more people and goods faster, cheaper, and with greater convenience. As air travel continues to grow, airports will face challenges in responding to increasing passenger vehicle traffic, which leads to lower operational efficiency, poor air quality, and security concerns. This paper evaluates methods for traffic demand forecasting combined with traffic microsimulation, which will allow airport operations staff to accurately predict traffic and congestion. Using two years of detailed data describing individual vehicle arrivals and departures, aircraft movements, and weather at Dallas-Fort Worth (DFW) International Airport, we evaluate multiple prediction methods including the Auto Regressive Integrated Moving Average (ARIMA) family of models, traditional machine learning models, and DeepAR, a modern recurrent neural network (RNN). We find that these algorithms are able to capture the diurnal trends in the surface traffic, and all do very well when predicting the next 30 minutes of demand. Longer forecast horizons are moderately effective, demonstrating the challenge of this problem and highlighting promising techniques as well as potential areas for improvement. Traffic demand is not the only factor that contributes to terminal congestion, because temporary changes to the road network, such as a lane closure, can make benign traffic demand highly congested. Combining a demand forecast with a traffic microsimulation framework provides a complete picture of traffic and its consequences. The result is an operational intelligence platform for exploring policy changes, as well as infrastructure expansion and disruption scenarios. To demonstrate the value of this approach, we present results from a case study at DFW Airport assessing the impact of a policy change for vehicle routing in high demand scenarios. This framework can assist airports like DFW as they tackle daily operational challenges, as well as explore the integration of emerging technology and expansion of their services into long term plans.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Synchronized Phasor Measurement Unit-based Central Controller for Normal and Contingent Operation of a High-Capacity HVDC Macrogrid for the Continental US

This paper presents a Synchronized Phasor Measurement Unit (PMU) based controller to support the coordination and operation of a high-capacity high-voltage direct current (HVDC) macrogrid transmission for the continental US. The proposed controller allows for optimal scheduling of each segment of the multi-terminal HVDC network under normal and contingent conditions, while considering minimum levels of frequency response requirements. The performance of the proposed controller is tested on a 100,222-bus representation of the US Eastern and Western interconnections. Results show that a centralized PMU-based controller improves the frequency nadir of the HVDC macrogrid under contingency conditions by 25.9%. Furthermore, the primary frequency response (PFR) of the HVDC macrogrid is increased by 33.4%. The performance of each interconnection under the largest credible contingency conditions is also discussed.

Mohan, Nihal↗
DOE OSTI2024

Evaluation of Clamshell Current Coupler for Online Frequency Domain and Spread Spectrum Time Domain Reflectometry to Detect Anomalies in Energized Cables

This document describes adaptation and evaluation of a clamshell inductive current coupler for online reflectometry testing (both frequency domain reflectometry and spread spectrum time domain reflectometry) to evaluate cable insulation degradation and anomalies. Safety-critical nuclear power plant cables were initially qualified for 40 years. However, as plants extend their operating licenses to 60 and 80 years, justification for continued safe operation includes test and monitoring programs. These will become more important as the industry moves to condition based qualification programs. Cable test programs traditionally involve manual interventions to disconnect cables, perform one or several tests, then reconnect the systems, usually during refueling outages occurring only every 18 to 24 months. This poses an operational burden that can be minimized by online testing or periodic connection to a coupler that may remain on the cable of interest or be clamped onto the cable without de-termination. This work investigates the adaptation of a clamshell inductive current coupler for either frequency domain reflectometry or spread-spectrum time domain reflectometry. The reflectometry test instrument injects a broad-band chirp or pseudo-noise signal onto a cable conductor and monitors for a reflected signal indicative of an impedance change caused by a damage condition. The instrument maximum input signal levels are typically 10 to 30 volts or less and the instruments will be damaged if subjected to 60 Hz power line voltages of 110, 220, or 480 VAC. One commercial spread-spectrum time domain reflectometry system has circuitry suitable for voltages up to 1 kV, but typical reflectometry tests are performed on de-energized cables. The clamshell inductive coupler provides >60 dB of 60 Hz attenuation with less than 10 dB loss in the 1-500 MHz test bandwidth of interest. An energized cable was successfully tested up to 6.7 kVp-p and frequency response plots imply that the tests could be extended to 10 kV or higher energized levels.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Route Optimization for Energy Efficient Airport Shuttle Operations - A Case Study from Dallas Fort Worth International Airport

Air travel and requisite surface traffic supporting passenger arrival/departure constitutes a significant portion of travel and emissions in cities with large airports. An airport trip can segment into three parts namely: i) travel from a location in the city to the airport; ii) travel from a parking lot or rental car center to the terminal (i.e., within the airport premises), and iii) travel inside the terminal. Depending on the airport access mode all or a part of these legs comprise a traveler’s journey to the airport. The priority of airport ground transport management teams is to provide passengers with a seamless travel experience within the airport, so it is understandable that within airport shuttle routes might not be optimized for minimizing energy consumption. Solutions that meet the dual objective of reducing energy consumption from airport shuttle operations without compromising on passenger travel experience are key to improving system efficiency. There is currently a dearth of research and tools that can inform airports in making such decisions. Addressing this need, this research effort puts forth an optimization model that generates optimal shuttle routes for a given set of constraints, and a discrete-event simulator that evaluates the optimal solutions in a stochastic environment to understand the tradeoffs between passenger wait times, and within airport shuttle energy consumption. The proposed set of tools are tested in the context of optimizing airport shuttles routes within the Dallas Fort Worth International Airport (DFW). In addition to shuttle spatial positioning, and passenger demand information, high-fidelity vehicle data was collected using data loggers installed on DFW shuttles. Results show that 20% energy reduction in shuttle operations is possible with a modest two-minute increase in average passenger wait times. The tools developed in this research effort are designed to be generalizable and can help optimize shuttle operations planning at any major airport.

air travel↗
DOE OSTI2026

High-Voltage Sodium–Metal Batteries with Asymmetric Fluoroalkoxylated Organoborate Anion Chemistry

The high reactivity of sodium (Na) metal restricts its compatibility to ether-based electrolytes, while the poor oxidative stability of ethers precludes their coupling to high-voltage cathodes, fundamentally limiting the operating voltage and energy density of sodium–metal batteries (SMBs). We present here a coordination-asymmetry strategy to reconcile this thermodynamic mismatch by generating in situ an asymmetric fluoroalkoxylated organoborate anion, [FB(OCH(CF 3 ) 2 ) 3 ] − (BOF – ), via a Lewis acid–base adduct reaction in ether electrolyte. The asymmetric ligand architecture differentiates oxidative and fluorination pathways: oxidizable B–O moieties mediate controlled interfacial reconstruction, whereas the terminal B–F units supply fluorine for chemical passivation. This self-adaptive chemistry yields nanoscale, conformal, compositionally graded interphases: a boron-oxide/boron-oxycarbide-rich cathode-electrolyte interphase (CEI) that mitigates ether oxidation and a bilayered inorganic–organic solid–electrolyte interphase (SEI) that regulates Na deposition. The nanostructured interphases enable highly reversible Na plating/stripping with an average Coulombic efficiency (CE) of 99.98% and sustain stable 4.3 V operation of anode-free SMBs in oxidation-prone ether electrolytes. Furthermore, this work establishes asymmetric boron coordination as a molecular-level design principle for creating chemically adaptive interphases that overcome the redox asymmetry in energy-dense electrochemical systems.

Anions↗
DOE OSTI2021

Dynamics of voltage-driven oscillating insulator-metal transitions

Recent experiments demonstrated emerging alternating insulator and metal phases in Mott insulators actuated by a direct bias voltage, leading to oscillating voltage outputs with characteristic frequencies. Here, we develop a physics-based nonequilibrium model to describe the dynamics of oscillating insulator-metal phase transitions and experimentally validate it using a VO 2 device as a prototype. The oscillation frequency is shown to scale monotonically with the bias voltage and series resistance and terminate abruptly at lower and upper device-dependent limits, which are dictated by the nonequilibrium carrier dynamics. Here, we derive an approximate analytical expression for the dependence of the frequency on the device operating parameters, which yields a fundamental limit to the frequency and may be utilized to provide guidance to potential applications of insulator-metal transition materials as building blocks of brain-inspired non-von Neumann computers.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Active Learning Framework

Machine learning (ML) of interatomic potentials show great promise to accelerate scientific simulation, e.g., by emulating expensive computations at a high accuracy but much reduced computational cost. Training datasets are calculated from computationally expensive ab initio quantum mechanics methods, density functional theory (DFT). Trained on this data, an ML model can be very successful in predicting energy and forces for new atomic configurations. A critical factor is the quality and diversity of the training dataset. Thus, a highly automated approach to dataset construction based on active learning framework is designed suitable for material physics. The active learning scheme begins with fully randomized atomic configurations. Then, many Molecular Dynamics (MD) trajectories are simulated using current ML potentials, where each MD trajectory is initialized to a random disordered configuration. The temperature is varied in order to diversify the sampled configuration during these simulations. The variance of predictions for eight neural networks within an ensemble is analyzed to determine whether the model is operating as expected. This helps in determining whether collecting more data would be helpful to the model by checking the ensemble variance is greater than the threshold. In this case, the MD trajectory is terminated and the final atomic configuration is placed on a queue (SQL database) for DFT calculations and added to training dataset. Periodically, ML model is retrained to the updated training model. This Active Learning loop is iterated until the cost of MD simulations becomes prohibitively expensive. The MD simulations will hopefully be sufficiently robust to support nucleation after many active learning iterations. In this sense, active learning scheme must automatically discover the important low energy and nonequilibrium physics.

Nebgen, Benjamin↗
DOE OSTI2023

Experimental Evaluation of Refrigerant Leak Characteristics for Different HVAC&R Equipment Types–Phase 2

The US Department of Energy (DOE) Building Technology Office (BTO) and the Air-conditioning, Heating & Refrigeration Technology Institute (AHRTI) collaborated to sponsor an experimental study of refrigerant leak characteristics at Oak Ridge National Laboratory (ORNL); AHRTI project 9012. The project has been conducted in two phases with objectives to conduct refrigerant leak tests on several heating, ventilating, air-conditioning and refrigeration (HVAC&R) systems under operating conditions representative of actual applications to document the pressure decay rate and the mass flow rate of leaked refrigerant as a function of time. Phase 1 of the project ran from late 2017 to late 2018 with refrigerant leaks imposed on five systems and the collection of data to meet the project objectives. Systems chosen covered three air-conditioning (AC) applications (packaged terminal AC or PTAC, 3-ton residential split system AC, and 5-ton packaged rooftop AC) and two refrigeration applications (split system unit cooler, and standalone display case). AHRTI members donated the test systems used for the project. The systems were tested at two different leak rates (catastrophic high rate simulating full line break and a lower flow rate), two leak locations (high-pressure side and low-pressure side), and two operating conditions (compressor ON or OFF). Phase 1 results were summarized in a project report by Baxter, et al. (2019)1. The leak rates imposed in Phase 1 led to much more rapid charge releases than the more typical much slower rates seen in practice that would take days, weeks, or months to empty a system of its entire charge. For Phase 2, the project sponsors asked that the “higher” leak rate target a total charge release time of about 4 min. This was intended to represent a “reasonable” worst case release scenario to match the refrigerant leak rate assumption used in the International Electrotechnical Commission (IEC) standard IEC 60335-2-40 (2016 version [IEC 2016]. A charge release time of about 20–40 min (leak release rate 5 to 10 times lower than higher rate) was targeted for the “lower” leak rate. This report provides a summary of the Phase 2 effort. Two additional HVAC systems were selected for testing in this phase. First was a multi-split air-conditioning (MS-AC) system with one outdoor section and two indoor units and a nameplate refrigerant charge of 1.75 kg (3.86 lb.) of R-410A. The MS-AC was tested in cooling only or AC operation. Second was a split system heat pump coupled to two different representative supply duct systems (HP-duct) and a nameplate charge of 3.83 kg (8.44 lb.) of R-410A. This system was tested in both space heating and AC modes. As in Phase 1 of the project, all tests were conducted using R-410A.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Optimal interconnection of three-terminal tandem solar cells

Three-terminal (3T) tandem solar cells require an adapted module integration scheme in order to explore their full efficiency potential. The three terminals allow to extract the power of the top and bottom cell separately. In a cell string, the wide bandgap top cells are interconnected in parallel to multiple bottom cells resulting in a parallel/series interconnection. This interconnection scheme affects the operation of the subcells, the resulting current path between the subcells, the layout of the cell interconnects, and the system level. Here, we analyze by simulations and experiments the aspects of the module integration of series- and reverse-connected 3T cells with their practical impact on module processes and performance as well as the effect of varying voltage ratios on the string-end losses. If the subcells are connected in series, the module integration requires insulation layers and significantly longer interconnects compared to devices with reverse-connected subcells. Tandem devices with a reverse connection and a voltage ratio between top and bottom cell of 2:1 allow a lean interconnection design and low integration losses. Here, we present an approach for the integration of bypass diodes for the protection against shading effects that allow to minimize string-end and shading losses for a system of modules featuring 3T cells.

14 SOLAR ENERGY↗
DOE OSTI2023

Explicit model predictive control through robust optimization

A strategy that calculates an explicit state feedback policy to regulate constrained uncertain discrete‐time uncertain linear systems is presented. We consider uncertain processes, affected by box‐bounded multiplicative uncertainty as well as bounded additive uncertainty with linear state and inputs constraints. The proposed method includes (i) the calculation of a terminal set constraint and (ii) the robust reformulation of state constraints in the prediction horizon. These features allow the derivation of the desired policy by solving a single multiparametric quadratic programming problem that guarantees feasible operation in the presence of uncertainty. Additionally, we employ variable and constraint elimination approaches to enhance the computational performance of the strategy. We demonstrate the steps and benefits of these developments with a numerical example and a chemical engineering case study.

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

HEMP Testing of Substation Yard Circuit Breaker Control and Protective Relay Circuits

There are concerns about the effects of High-Altitude Electromagnetic Pulses (HEMP) on the electric power grid. Activities to date tested and analyzed vulnerability of digital protective relays (DPRs) used in power substations, but the effect of HEMP on the greater substation environment is not well known. This work establishes a method of testing the vulnerability of circuit breaker control and protective relay circuits to the radiated E1 pulse associated with HEMP based on coupling to the cables in a substation yard. Two DPRs from Schweitzer Engineering Laboratories, Inc. were independently tested. The test setup also included a typical cable in a substation yard with return plane to emulate the ground grid and other ground conductors near the yard cable, cabinetry housing the installed DPRs, station battery and battery charger, terminal block elements, and a breaker simulator to emulate a substation yard configuration. The DPRs were powered from the station battery and the transformer inputs energized with a three-phase source to maintain typical operating conditions during the tests. Vulnerability testing consisted of a conducted E1 pulse injected into the center of the yard cable of the DPR circuits. Current measurements on the yard cable and DPR inputs indicated significant attenuation of the conducted pulse arriving at the control house equipment from the emulated substation yard. This reduction was quantified with respect to the equivalent open-circuit voltage on the yard cable. No equipment damage or undesired operation occurred on the tested circuits for values below 180 kV, which is significantly higher than the anticipated coupling to a substation yard cable.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2024

Building ControlScore: General Service Administration Office Building Deployment

Improvements to building control systems can lead to energy savings and increased occupant comfort. In an optimized system, process variables such as air temperature will closely follow their desired setpoints and avoid excess energy use. Typically, experts must manually inspect individual control loops to identify poor performance and opportunities for improvement. However, this approach is difficult in modern buildings that have a prohibitively large number of controllers. To address this issue, Pacific Northwest National Laboratory (PNNL) created the ControlScore concept, which takes operating data from the many controllers within a building and generates standardized scores for each loop on a scale of 0 to 10 (a score of 0 indicates poor control, a score of 10 indicates good control). PNNL applied the Building ControlScore application to all available data from a General Services Administration office building within the period of January 1, 2023, to March 9, 2023. The building scored a 4.7 overall, with all 74 of the building’s loops fitting a roughly normal distribution centered around 5. These results indicate that the analyzed systems have below-average performance with room for improvement, especially in the poorly scored systems. Airflow loops tended to have much lower scores than zone temperature loops. The lowest and highest performing systems in the building section were identified, as were all loops with a score less than 1. While the ControlScore identifies loops and systems that aren’t meeting their designated setpoints, it does not indicate the cause of those issues. For example, consider a supply air terminal unit’s airflow loop that received a low score due to it delivering less air than specified by the setpoint. The lower-than-desired airflow could be due to equipment limitations (e.g., the terminal unit or duct serving is too small to accommodate that airflow), malfunctioning equipment (e.g., a stuck damper or bad sensor), or something else entirely. The ControlScore does not diagnose problems it simply identifies the symptoms that can be explored and addressed by building operators.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2025

Enhancing the solubility of SARS-CoV-2 inhibitors to increase future prospects for clinical development

SARS-CoV-2 poses an ongoing threat to human health as variants continue to emerge. Several effective vaccines are available, but a diminishing number of Americans receive the updated vaccines (only 22% received the 2023 update). Public hesitancy towards vaccines and common occurrence of “breakthrough” infections (i.e., infections of vaccinated individuals) highlight the need for alternative methods to reduce viral transmission. SARS-CoV-2 enters cells by fusing its envelope with the target cell membrane in a process mediated by the viral spike protein, S. The S protein operates via a Class I fusion mechanism in which fusion between the viral envelope and host cell membrane is mediated by structural rearrangements of the S trimer. We previously reported lipopeptides derived from the C-terminal heptad repeat (HRC) domain of SARS-CoV-2 S that potently inhibit fusion by SARS-CoV-2, both in vitro and in vivo. These lipopeptides bear an attached cholesterol unit to anchor them in the membrane. Here, to improve prospects for experimental development and future clinical utility, we employed structure-guided design to incorporate charged residues at specific sites in the peptide to enhance aqueous solubility. This effort resulted in two new, potent lipopeptide inhibitors.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Electrochemical Oxidation of Organic Molecules at Lower Overpotential: Accessing Broader Functional Group Compatibility with Electron-Proton Transfer Mediators

CONSPECTUS: Electrochemical organic oxidation reactions are highly appealing because protons are often effective terminal electron acceptors, thereby avoiding undesirable stoichiometric oxidants. These reactions are often plagued by high overpotentials, however, that greatly limit their utility. Single-electron transfer (SET) from organic molecules generates high energy radical-cations. Formation of such intermediates often requires electrode potentials far above the thermodynamic potentials of the reaction and frequently causes decomposition and/or side reactions of ancillary functional groups. In this Account, we show how electrocatalytic electron-proton transfer mediators (EPTMs) address this challenge. EPTMs bypass the formation of radical-cation intermediates by supporting mechanisms that operate at electrode potentials much lower (=1 V) than analogous direct electrolysis reactions. The stable aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidine N-oxyl) is an effective mediator for electrochemical alcohol oxidation, and we have employed such processes for applications ranging from pharmaceutical synthesis to biomass conversion. A complementary electrochemical alcohol oxidation method employs a cooperative Cu/TEMPO mediator system that operates at 0.5 V lower electrode potential than the TEMPO-only mediated process. This difference, which arises from a different catalytic mechanism, rationalizes the broad functional group tolerance of Cu/TEMPO-based aerobic alcohol oxidation catalysts. Aminoxyl mediators address long-standing challenges in the "Shono oxidation", an important method for a-C–H oxidation of tertiary amides and carbamates. Shono oxidations are initiated by a high-potential SET step that limits their utility. Aminoxyl-mediated Shono-type oxidations have been developed that operate at much lower potentials and tolerate diverse functional groups. Analogous reactivity underlies a-C–H cyanation of secondary cyclic amines, a new method that enables efficient diversification of piperidine-based pharmaceutical building blocks and preparation of non-natural amino acids. Electrochemical oxidations of benzylic C–H bonds are commonly initiated by SET to generate radical cations, but such methods are again plagued by large overpotentials. Mediated electrolysis methods that promote hydrogen-atom-transfer (HAT) from benzylic C–H bonds to Fe-oxo species and phthalimide N-oxyl (PINO) support C–H oxygenation, iodination, and oxidative-coupling reactions. A complementary method merges photochemistry with electrochemistry to achieve amidation of C(sp3)–H bonds. This unique process operates at much lower overpotentials compatible with diverse functional groups. These results have broad implications for organic electrochemistry, highlighting the importance of "overpotential" considerations and the prospects for expanding synthetic utility by using mediators to bypass high-energy outer-sphere electron-transfer mechanisms. Principles demonstrated here for oxidation are equally relevant to electrochemical reductions.

Wang, Fei↗
DOE OSTI2021

Fundamentals of Three-Terminal Tandem Solar Cells: a Comprehensive Taxonomy

Three-terminal tandem (3TT) solar cells can overcome some of the limitations of two- and four-terminal tandem designs. However, the coupled nature of the cells adds a degree of complexity to the devices themselves and the ways that their performance can be measured and reported. To facilitate understanding, we have developed a taxonomy which encompasses all types of 3TT devices, enabling a common nomenclature for discussing devices and performance. Once the physical devices, contact nodes, and loading circuitry have been self-consistently described, it becomes apparent that a wide range of 3TT devices share a common set of design and operating principles.

3T↗