Search NASA⌕ Search

SEARCH · Search NASA

Results for “complex cycling conditions”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 37 records · Page 2

Comparison of Forced ENSO-Like Hydrological Expressions in Simulations of the Preindustrial and Mid-Holocene

Using the water isotope- and vapor source distribution (VSD) tracer-enabled Goddard Institute for Space Studies ModelE-R, we examine changing El Nino-Southern Oscillation (ENSO)-like expressions in the hydrological cycle in a suite of model experiments. We apply strong surface temperature anomalies associated with composite observed El Nino and La Nina events as surface boundary conditions to preindustrial and mid-Holocene model experiments in order to investigate ENSO-like expressions in the hydrological cycle under varying boundary conditions. We find distinct simulated hydrological anomalies associated with El Nino-like ("ENSOWARM") and La Nina-like ("ENSOCOOL") conditions, and the region-specific VSD tracers show hydrological differences across the Pacific basin between El Nino-like and La Nina-like events. The application of ENSOCOOL forcings does not produce climatological anomalies that represent the equal but opposite impacts of the ENSOWARM experiment, as the isotopic anomalies associated with ENSOWARM conditions are generally stronger than with ENSOCOOL and the spatial patterns of change distinct. Also, when the same ENSO-like surface temperature anomalies are imposed on the mid-Holocene, the hydrological response is muted, relative to the preindustrial. Mid-Holocene changes in moisture sources to the analyzed regions across the Pacific reveal potentially complex relationships between ENSO-like conditions and boundary conditions. Given the complex impacts of ENSO-like conditions on various aspects of the hydrological cycle, we suggest that proxy record insights into paleo-ENSO variability are most likely to be robust when synthesized from a network of many spatially diverse archives, which can account for the potential nonstationarity of ENSO teleconnections under different boundary conditions.

boundary conditions↗

Thermal High- and Low-Cycle Fatigue Behavior of Thick Thermal Barrier Coating Systems

Ceramic thermal barrier coatings have received increasing attention for advanced gas turbine and diesel engine applications because of their ability to provide thermal insulation to engine components. However, the durability of these coatings under the severe thermal cycling conditions encountered in a diesel engine (ref. 1) still remains a major issue. In this research at the NASA Lewis Research Center, a high-power laser was used to investigate the thermal fatigue behavior of a yttria-stabilized zirconia coating system under simulated diesel engine conditions. The mechanisms of fatigue crack initiation and propagation, and of coating failure under complex thermal low-cycle fatigue (LCF, representing stop/start cycles) and thermal high-cycle fatigue (HCF, representing operation at 1300 rpm) are described. Continuous wave and pulse laser modes were used to simulate pure LCF and combined LCF/HCF, respectively (ref. 2). The LCF mechanism was found to be closely related to the coating sintering and creep at high temperatures. These creep strains in the ceramic coating led to a tensile stress state during cooling, thus providing the major driving force for crack growth under LCF conditions. The combined LCF/HCF tests induced more severe coating surface cracking, microspallation, and accelerated crack growth than did the pure LCF test. HCF thermal loads also facilitated lateral crack branching and ceramic/bond coat interface delaminations. HCF is associated with the cyclic stresses originating from the high-frequency temperature fluctuation at the ceramic coating surface. The HCF thermal loads act on the crack by a wedging mechanism (ref. 1), resulting in continuous crack growth at temperature. The HCF stress intensity factor amplitude increases with the interaction depth and temperature swing, and decreases with the crack depth. HCF damage also increases with the thermal expansion coefficient and the Young's modulus of the ceramic coating (refs. 1 and 3).

Miller, Robert A.↗

Reactions of Studtite UO 4 ·4H 2 O in Alkali Hydroxides: Isolation of Single-Crystal Uranate Phases under Mild Hydrothermal Conditions

Uranyl peroxide complexes, particularly studtite (UO 4 ·4H 2 O), are important phases within the nuclear fuel cycle, forming through radiolysis-induced reactions on the surfaces of spent fuel and in waste environments. Studtite has been identified in Hanford’s irradiated fuel storage basins, Chornobyl’s corium lavas, and is anticipated on Fukushima’s fuel debris. While its formation and stability have been extensively studied, the reactivity of UO 4 ·4H 2 O in highly alkaline environments such as those encountered in high-level nuclear waste remains underexplored. These environments contain molar concentrations of [OH - ] and present a chemically dynamic and reactive environment where actinide behavior is not well understood. Reported here are investigations of uranium reactions in concentrated alkali hydroxides under mild hydrothermal conditions (<200 °C) that have resulted in the isolation of the alkali metal uranates Li 2 UO 4 , α-Na 2 UO 4 , γ-Na 2 U 2 O 7 , and K 2 U 2 O 7 . In contrast to conventional solid-state methods (>800 °C) that typically yield polycrystalline powders, our approach enables the isolation of these uranates as single crystals, allowing us to provide single-crystal structure solutions of certain uranates for the first time. Our findings match the results of high-level waste tank sampling, confirming that sodium diuranate (Na 2 U 2 O 7 ) is the most persistent uranium phase, potentially forming through reactions of uranyl peroxide intermediates with NaOH under radiolytic and highly alkaline conditions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Radiolytic evaluation of acetohydroxamic acid (AHA) under biphasic (n-dodecane and TBP/DEHBA/DEHiBA) used nuclear fuel reprocessing conditions

Acetohydroxamic acid (AHA) has been proposed as a substitute for uranium(IV) and hydrazine as a plutonium complexant and neptunium reductant for simplified, single-cycle used nuclear fuel reprocessing flowsheets. However, the chemical behavior of AHA in an intense multi-component radiation field is poorly understood, especially under representative biphasic reprocessing solvent system conditions. In response to this critical knowledge gap, this study has investigated the gamma radiolytic integrity of AHA in aqueous nitric solutions in contact with an organic phase, comprising current and future reprocessing ligands (TBP, DEHBA, and DEHiBA) dissolved in n-dodecane diluent. Our data show negligible effect of the organic phase on the radiolytic behavior of AHA compared to complementary single-phase experiments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Multipoint Variable Cycle Engine Design Using Gradient-based Optimization

Supersonic aircraft are challenging to optimally design due to the widely varying constraints and flight conditions they experience. Additionally, a large number of disciplinary subsystems must be considered due to highly complex design requirements. One subsystem that has a major effect on overall performance is the engine. In this work, we construct a supersonic mixed-flow variable cycle engine and perform multipoint gradient-based optimization using this model. We see that the operational variables allow the optimizer to tailor performance at each individual flight condition, leading to better overall performance. To simulate airframe integration constraints, we run successive optimizations with increasingly restrictive inlet areas and see decreases in engine performance. This work is part of a larger effort to incorporate engine design into aero-thermal-mission optimization of a supersonic aircraft.

Cycle analysis↗

Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

Air pollution↗

The Role of Pulse Radiolysis in Advanced Nuclear Fuel Cycles

The effects of ionizing radiation are ubiquitous throughout all aspects of a nuclear fuel cycle. The complexity and intensity of these effects are greatest during reactor operations and in the management of used nuclear fuel and waste. Radiation-induced processes typically promote the chemical transformation of molecules and materials with the formation of potentially detrimental degradation products and corresponding changes in physical and chemical properties, which ultimately impact the effectiveness and longevity of nuclear technologies. Consequently, a molecular-level understanding of radiation effects over multiple time, distance, and material domains is essential for the innovation and deployment of next generation nuclear technologies. Attaining this knowledge necessitates a firm grasp of radiation-induced reaction kinetics, for which pulsed electron radiolysis is the methodology of choice. Presented here are several recent studies from our group that demonstrate the critical role of pulsed electron radiolysis techniques in the advancement of our understanding of radiation-induced chemistry under advanced nuclear fuel cycle conditions. Research topics include late actinide redox chemistry, radiation robustness of used nuclear fuel reprocessing complexants, and the behavior of metal cations in high temperature molten salt media.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

ActinoBase: tools and protocols for researchers working on Streptomyces and other filamentous actinobacteria

Actinobacteria is an ancient phylum of Gram-positive bacteria with a characteristic high GC content to their DNA. The ActinoBase Wiki is focused on the filamentous actinobacteria, such as Streptomyces species, and the techniques and growth conditions used to study them. These organisms are studied because of their complex developmental life cycles and diverse specialised metabolism which produces many of the antibiotics currently used in the clinic. ActinoBase is a community effort that provides valuable and freely accessible resources, including protocols and practical information about filamentous actinobacteria. It is aimed at enabling knowledge exchange between members of the international research community working with these fascinating bacteria. ActinoBase is an anchor platform that underpins worldwide efforts to understand the ecology, biology and metabolic potential of these organisms. There are two key differences that set ActinoBase apart from other Wiki-based platforms: [1] ActinoBase is specifically aimed at researchers working on filamentous actinobacteria and is tailored to help users overcome challenges working with these bacteria and [2] it provides a freely accessible resource with global networking opportunities for researchers with a broad range of experience in this field.

59 BASIC BIOLOGICAL SCIENCES↗

We Must Stop Fossil Fuel Emissions to Protect Permafrost Ecosystems

Climate change is an existential threat to the vast global permafrost domain. The diverse human cultures, ecological communities, and biogeochemical cycles of this tenth of the planet depend on the persistence of frozen conditions. The complexity, immensity, and remoteness of permafrost ecosystems make it difficult to grasp how quickly things are changing and what can be done about it. Here, we summarize terrestrial and marine changes in the permafrost domain with an eye toward global policy. While many questions remain, we know that continued fossil fuel burning is incompatible with the continued existence of the permafrost domain as we know it. If we fail to protect permafrost ecosystems, the consequences for human rights, biosphere integrity, and global climate will be severe. The policy implications are clear: the faster we reduce human emissions and draw down atmospheric CO 2 , the more of the permafrost domain we can save. Emissions reduction targets must be strengthened and accompanied by support for local peoples to protect intact ecological communities and natural carbon sinks within the permafrost domain. Some proposed geoengineering interventions such as solar shading, surface albedo modification, and vegetation manipulations are unproven and may exacerbate environmental injustice without providing lasting protection. Conversely, astounding advances in renewable energy have reopened viable pathways to halve human greenhouse gas emissions by 2030 and effectively stop them well before 2050. We call on leaders, corporations, researchers, and citizens everywhere to acknowledge the global importance of the permafrost domain and work towards climate restoration and empowerment of Indigenous and immigrant communities in these regions.

54 ENVIRONMENTAL SCIENCES↗

Dilute Combustion Control Using Spiking Neural Networks

Dilute combustion with exhaust gas recirculation (EGR) in spark-ignition engines presents a cost-effective method for achieving higher levels of engine efficiency. At high levels of EGR, however, cycle-to-cycle variability (CCV) of the combustion process is exacerbated by sporadic occurrences of misfires and partial burns. Previous studies have shown that temporal deterministic patterns emerge at such conditions and certain combustion cycles have a significant influence over future events. Due to the complexity of the combustion process and the nature of CCV, harnessing all the deterministic information for control purposes has remained challenging even with physics based 0-D, 1-D, and high-fidelity computational fluid dynamics (CFD) models. In this study, we present a data-driven approach to optimize the combustion process by controlling CCV adjusting the cycle-to-cycle fuel injection quantity. Readily available data from in-cylinder pressure was used to train a spiking neural network (SNN) which learns the optimal way to manage fuel injection in order to reduce CCV while maintaining acceptable levels of fuel consumption. SNNs are particularly well suited for powertrain control applications due to their ability to be deployed on FPGA-based neuromorphic hardware which are small, inexpensive, and have a low power demand. The high-performance computing (HPC) resources of Oak Ridge National Laboratory were used to run an evolutionary-based training approach for choosing the best SNN configuration that minimizes the size of the network while achieving the desired goal. The neuromorphic hardware with the optimized SNN deployed was connected to the rapid prototyping engine control system for real-time control implementation and tested on a single cylinder version of a GM LNF 4-cylinder engine. The results show a significant reduction of CCV with a small percentage of additional fuel used to stabilize the charge.

33 ADVANCED PROPULSION SYSTEMS↗

Service Life Extension of the Propulsion System of Long-Term Manned Orbital Stations

One of the critical non-replaceable systems of a long-term manned orbital station is the propulsion system. Since the propulsion system operates beginning with the launch of station elements into orbit, its service life determines the service life of the station overall. Weighing almost a million pounds, the International Space Station (ISS) is about four times as large as the Russian space station Mir and about five times as large as the U.S. Skylab. Constructed over a span of more than a decade with the help of over 100 space flights, elements and modules of the ISS provide more research space than any spacecraft ever built. Originally envisaged for a service life of fifteen years, this Earth orbiting laboratory has been in orbit since 1998. Some elements that have been launched later in the assembly sequence were not yet built when the first elements were placed in orbit. Hence, some of the early modules that were launched at the inception of the program were already nearing the end of their design life when the ISS was finally ready and operational. To maximize the return on global investments on ISS, it is essential for the valuable research on ISS to continue as long as the station can be sustained safely in orbit. This paper describes the work performed to extend the service life of the ISS propulsion system. A system comprises of many components with varying failure rates. Reliability of a system is the probability that it will perform its intended function under encountered operating conditions, for a specified period of time. As we are interested in finding out how reliable a system would be in the future, reliability expressed as a function of time provides valuable insight. In a hypothetical bathtub shaped failure rate curve, the failure rate, defined as the number of failures per unit time that a currently healthy component will suffer in a given future time interval, decreases during infant-mortality period, stays nearly constant during the service life and increases at the end when the design service life ends and wear-out phase begins. However, the component failure rates do not remain constant over the entire cycle life. The failure rate depends on various factors such as design complexity, current age of the component, operating conditions, severity of environmental stress factors, etc. Development, qualification and acceptance test processes provide rigorous screening of components to weed out imperfections that might otherwise cause infant mortality failures. If sufficient samples are tested to failure, the failure time versus failure quantity can be analyzed statistically to develop a failure probability distribution function (PDF), a statistical model of the probability of failure versus time. Driven by cost and schedule constraints however, spacecraft components are generally not tested in large numbers. Uncertainties in failure rate and remaining life estimates increase when fewer units are tested. To account for this, spacecraft operators prefer to limit useful operations to a period shorter than the maximum demonstrated service life of the weakest component. Running each component to its failure to determine the maximum possible service life of a system can become overly expensive and impractical. Spacecraft operators therefore, specify the required service life and an acceptable factor of safety (FOS). The designers use these requirements to limit the life test duration. Midway through the design life, when benefits justify additional investments, supplementary life test may be performed to demonstrate the capability to safely extend the service life of the system. An innovative approach is required to evaluate the entire system, without having to go through an elaborate test program of propulsion system elements. Evaluating every component through a brute force test program would be a cost prohibitive and time consuming endeavor. ISS propulsion system components were designed and built decades ago. There are no representative ground test articles for some of the components. A 'test everything' approach would require manufacturing new test articles. The paper outlines some of the techniques used for selective testing, by way of cherry picking candidate components based on failure mode effects analysis, system level impacts, hazard analysis, etc. The type of testing required for extending the service life depends on the design and criticality of the component, failure modes and failure mechanisms, life cycle margin provided by the original certification, operational and environmental stresses encountered, etc. When specific failure mechanism being considered and the underlying relationship of that mode to the stresses provided in the test can be correlated by supporting analysis, time and effort required for conducting life extension testing can be significantly reduced. Exposure to corrosive propellants over long periods of time, for instance, lead to specific failure mechanisms in several components used in the propulsion system. Using Arrhenius model, which is tied to chemically dependent failure mechanisms such as corrosion or chemical reactions, it is possible to subject carefully selected test articles to accelerated life test. Arrhenius model reflects the proportional relationship between time to failure of a component and the exponential of the inverse of absolute temperature acting on the component. The acceleration factor is used to perform tests at higher stresses that allow direct correlation between the times to failure at a high test temperature to the temperatures to be expected in actual use. As long as the temperatures are such that new failure mechanisms are not introduced, this becomes a very useful method for testing to failure a relatively small sample of items for a much shorter amount of time. In this article, based on the example of the propulsion system of the first ISS module Zarya, theoretical approaches and practical activities of extending the service life of the propulsion system are reviewed with the goal of determining the maximum duration of its safe operation.

Kamath, Ulhas↗

Reversible solid oxide cells: Early performance and microstructural evolution during electrolysis and switched mode operation

Incorporating more renewables into our energy mix will require a diversity of technological solutions. Reversible solid oxide cell systems (RSOCs) operating reversibly between fuel cell and electrolysis modes with high round-trip efficiencies offer one such solution. However, questions remain about the stability of the oxygen and fuel electrodes under reversible operation. Here, in this study, single cells with the configuration Ni-YSZ|YSZ|GDC10|NNO-NDC50|NNO are operated by reversible cycling under potentiostatic conditions. Test conditions are chosen to be representative of average stack conditions that are likely to be encountered during operation of a stack constructed of such cells. The results of reversible cycling over 500 h (21 cycles) are compared with operating the cells under potentiostatic conditions in the electrolysis-only mode (i.e., without cycling). Voltage-current density (DC), AC complex impedance spectroscopy, distribution of relaxation times (DRT) analysis, and scanning electron microscopy (SEM) indicate excellent reversibility and stability of the neodymium nickelate-based oxygen electrodes in both electrolysis and reversible cycling modes. Degradation behavior is attributed to the loss and coarsening of connected Ni particles in the fuel electrode, particularly in the active layer. However, reversible operation mitigates this degradation compared to operation in the electrolysis-only (SOEC-only) mode.

25 ENERGY STORAGE↗

Lidar-Based Evaluation of HRRR Performance in California’s Diablo Range

The performance of the NOAA High-Resolution Rapid Refresh (HRRR) model for capturing low-level winds near a wind energy production site during summer 2019 is evaluated. This study catalogs the ability of HRRR to predict boundary layer dynamics relevant to wind energy interests over complex terrain, which has presented challenges for weather and energy forecasting. Performance is evaluated by comparing HRRR output to wind-profiling Doppler lidars at Lawrence Livermore National Laboratory Site 300. HRRR captured the diurnal profile of horizontal winds in the observed 150-m layer, despite strong underpredictions (∼4 m s −1 ) during evening and nighttime hours. These underpredictions may be a result of local speedup flows observed by the lidars, which were unresolved in HRRR due to their small spatial extent. HRRR bias magnitude relative to observations was found to be minimal during days with synoptic-scale troughs and strong 850-hPa geopotential gradients, while bias magnitude was maximal during days with synoptic ridging and weak 850-hPa geopotential gradients. To translate wind speed predictions to energy forecasting, generic turbine models were used to estimate power generation for turbines characteristic of the nearby Altamont Pass Wind Resource Area. Results show that HRRR-based energy estimates predicted daytime power generation adequately relative to lidar-based estimates with an 18-h lead time (bias magnitude < 0.4 MW from 0900 to 1400 LT) but overpredicted power during the rest of the diurnal cycle (bias > 1 MW). These results demonstrate conditions under which HRRR performs well for wind energy applications in complex terrain, while highlighting biases that require further investigation to support usage of a high-resolution model for wind energy forecasts.

Boundary layer↗

Chemical Climatology of Atmospheric Pollutants in the Eastern United States: Seasonal/Diurnal Cycles and Contrast Under Clear/Cloudy Conditions for Remote Sensing

We statistically assessed temporal variations of observed concentrations of eight atmospheric pollutants (SO2, NO, NO2, NO(y), O3, CO, NH3, and HNO3) at three urban sites and one rural site in the eastern United States for a ten-year period (4 years for NH3). Diurnal/seasonal patterns of observed mean concentrations and their decade-scale trends under different weather conditions were evaluated. Concentrations of pollutants decreased consistently during the observation period (as long as 1997–2013), although nighttime ozone during winter appears to increase because of reduced NO-O3 titration. This study shows that the decay time of major air pollutant concentrations such as SO2 and NO(x) can be short as a few hours to one day. We also identified substantial differences between the mean concentrations of pollutants at clear sky and overcast conditions that could introduce biases into satellite observations. Surface concentrations of SO2 and CO are distinctly higher under cloud free than under overcast conditions by ∼30% and ∼20% respectively. NO2 shows a complex pattern, but demonstrates lower daytime concentrations under cloud-free skies. All of these estimates are important for understanding the chemical climatology of these atmospheric pollutants, especially their diurnal/seasonal cycles under different weather conditions. For four-year measurements, NH3 shows a substantial difference, with clear sky observations roughly a factor of two higher than those under overcast conditions. To track changes in the future, the full daily cycle of atmospheric pollutants monitored by geostationary satellite such as the future TEMPO mission may better capture patterns and trends.

TEMPO↗

Fatigue behavior of flexhoses and bellows due to flow-induced vibrations

The analysis and results developed in a fresh approach to calculate flow induced vibration response of a flexible flow passage are summarized. The vibration results are further examined in the frequency domain to obtain dominant frequency information. A cumulative damage analysis due to cyclic strains is performed to obtain the number of cycles to failure for a metallic bellows of particular specifications under a variety of operational conditions. Sample plots of time and frequency domain responses are included. The complex listing of a computer program is provided. The program successively executes each of the analyses needed to calculate the vibration response, the frequency response, the cyclic strains and the number of cycles to failure. The program prompts the user for necessary input information. Sample data from the program is provided. The fatigue life results obtained by the computer model lie within an acceptable range of previously measured available data.

Desai, P. V.↗

Experimental Protocols for Studying Organic Non-aqueous Redox Flow Batteries

We report that Redox flow batteries (RFBs) are promising devices for grid-scale energy storage due to the decoupling of power and energy, which can be independently scaled by the electrode area and storage tank size, respectively. To date, only aqueous RFBs, such as the vanadium RFB, have been implemented commercially. Nevertheless, the limited energy densities and high-cost materials may preclude their wider market penetration. Organic non-aqueous redox-flow batteries (O-NRFBs), which utilize redox-active organic molecules (ROMs), have been offered as an attractive alternative. Many possible advantages include the use of earth-abundant elements (C, H, N, O, S, F), wherein the ROMs can be prepared from low-cost and sustainable materials. Additionally, a large variety of electroactive moieties are accessible as building blocks, providing a synthetic platform to tune the properties of ROMs through rational design. As a consequence, the development of novel ROMs has attracted researchers with diverse backgrounds, prompting remarkable innovations in the past decade. However, consistency in experimental protocols (e.g., electrochemical methods, cycling stability, experimental conditions) has not coincided with this uptick in research, leading to sometimes ambiguous and incomparable results. This is further convoluted by the complexity innate to battery development, such as cell design, detection, and characterization of reactions and active components. The O-NRFB application imposes stringent requirements on the physical or/and chemical processes involved in electrochemical cycling. Yet such considerations are often overlooked. Further, while quantum mechanical calculations provide a convenient tool for evaluating and selecting ROM candidates, this simulation is not always performed. Thus, in this Energy Focus, we detail a means to standardize experimental protocols for studies of O-NRFBs and suggest practices to facilitate fundamental understanding and development of ROMs.

25 ENERGY STORAGE↗

Understanding the Role of Zinc Hydroxide Sulfate and its Analogues in Mildly Acidic Aqueous Zinc Batteries: A Review

Abstract Mildly acidic aqueous zinc batteries (AZBs) have attracted tremendous attention for grid storage applications with the expectation to tackle the issues of Li‐ion batteries on high cost and poor safety. However, the performance, particularly energy density and cycle stability of AZBs are still unsatisfactory when compared with LIBs. To help the development of AZBs, a lot of effort have been made to understand the battery reaction mechanisms and precedent microscopic and spectroscopic analyses have shown flake‐like large particles of zinc hydroxide sulfate (ZHS) and its analogues formed on the surfaces of cathodes and anodes in sulfate and other electrolyte systems during cycling. However, because of the complexity of the thermodynamics and kinetics of aqueous reactions to understand different battery conditions, controversies still exist. This article will review the roles of ZHS discussed in recent representative references aiming to shine light on the fundamental mechanisms of AZBs and pave ways to further improve the battery performance.

25 ENERGY STORAGE↗

Operando Mechanistic Studies of CO 2 Hydrogenation by Ruthenium Complexes Using High-Pressure NMR Spectroscopy

As a result of increased energy demands, the ability to both reduce carbon dioxide with dihydrogen to formate and conduct the reverse reaction with the same catalyst is of interest as a method for potential fuel generation and use. Ruthenium bis(diphosphine) complexes with and without pendant amines were reacted with mixtures of CO 2 /H 2 gases in the presence of added base to catalytically yield formate; when the base was triethylamine, the reaction was found to be reversible. The reactions were monitored using high-pressure operando 1 H and 31 P{ 1 H} NMR spectroscopy at 18 °C in THF under 40 atm of a 1:1 mixture of H 2 and CO 2 . The rate of production of formate was correlated with the observation of specific organometallic species by NMR spectroscopy under catalytic conditions, including a hydrido–dihydrogen complex. From this operando study, a mechanism is proposed with two competing catalytic cycles for which the predominant cycle is dependent on which base and catalyst are used. Finally, the role of the base is shown to be vital for both catalytic rate and reversibility of the chemical transformation, indicating base selection should be carefully considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗