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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Evaluation of Leading Modes of Climate Variability in the CMIP Archives

The adequate simulation of internal climate variability is key for our understanding of climate as it underpins efforts to attribute historical events, predict on seasonal and decadal time scales, and isolate the effects of climate change. Here the skill of models in reproducing observed modes of climate variability is assessed, both across and within the CMIP3, CMIP5, and CMIP6 archives, in order to document model capabilities, progress across ensembles, and persisting biases. A focus is given to the well-observed tropical and extratropical modes that exhibit small intrinsic variability relative to model structural uncertainty. These include El Niño–Southern Oscillation (ENSO), the Pacific decadal oscillation (PDO), the North Atlantic Oscillation (NAO), and the northern and southern annular modes (NAM and SAM). Significant improvements are identified in models’ representation of many modes. Canonical biases, which involve both amplitudes and patterns, are generally reduced across model generations. For example, biases in ENSO-related equatorial Pacific sea surface temperature, which extend too far westward, and associated atmospheric teleconnections, which are too weak, are reduced. Stronger tropical expression of the PDO in successive CMIP generations has characterized their improvement, with some CMIP6 models generating patterns that lie within the range of observed estimates. For the NAO, NAM, and SAM, pattern correlations with observations are generally higher than for other modes and slight improvements are identified across successive model generations. Finally, for ENSO and PDO spectra and extratropical modes, changes are small compared to internal variability, precluding definitive statements regarding improvement.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Compound Drought and Heatwaves at a Global Scale: The Role of Natural Climate Variability-Associated Synoptic Patterns and Land-Surface Energy Budget Anomalies

Compound drought and heatwave (CDHW) events have garnered much attention in recent studies. However, thus far, the identification of such events is oversimplified, and their association with natural climate variability is not fully explored. Here, we derive anomalies in the weekly self-calibrated Palmer Drought Severity Index (sc_PDSI) and daily maximum temperatures to identify CDHW events from 1982 to 2016 over 26 climate regions across the globe. Using a Poisson Generalized Linear Model (GLM), we analyze yearly occurrences of seasonal CDHW events and their association with the warm and cold phases of El Nino Southern Oscillation (ENSO), Pacific Decadal Oscillation (PDO), and North Atlantic Oscillation (NAO). ENSO exhibits robust association with CDHW events over the Southern Hemisphere during the austral summer and fall, while PDO influences their occurrences over the Western North America in the Northern Hemisphere during the boreal summer, which is supported by the composites of anomalies in the atmospheric circulations and surface energy budget. However, NAO association with CDHW events is relatively weak. The CDHW occurrence over other regions is driven by a combination of these large-scale natural forcing. Our analyses also highlight that the cooccurrence of weekly to submonthly scale anomalies in the observed temperature and precipitation may not be always aligned between the observations and the reanalysis. Therefore, caution must be exercised while explaining such observed anomalies on the basis of reanalysis-based circulations and surface energy budget. Lastly, our analyses provide a new insight towards concurrent extremes and should help foster research efforts in this area.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Revealing the Chemical State of Palladium in Operating In 2 O 3 Gas Sensors: Metallic Pd Enhances Sensing Response and Intermetallic In x Pd y Compound Blocks It

The sensing response of metal oxides activated with noble metal nanoparticles is significantly influenced by changes to the chemical state of corresponding elements under operating conditions. Here, a PdO/rh-In 2 O3 consisting of PdO nanoparticles loaded onto rhombohedral In 2 O 3 was studied as a gas sensor for H 2 gas (100–40000 ppm in an oxygen-free atmosphere) in the temperature range of 25–450 °C. The phase composition and chemical state of elements were examined by resistance measurements combined with synchrotron-based in situ X-ray diffraction and ex situ X-ray photoelectron spectroscopy. As found, PdO/rh-In 2 O 3 undergoes a series of structural and chemical transformations during operation: from PdO to Pd/PdH x and finally to the intermetallic In x Pd y phase. The maximal sensing response (R N2 /R H2 ) of ~5 · 10 7 towards 40000 ppm (4 vol %) H 2 at 70 °C is correlated with the formation of PdH 0.706 /Pd. The In x Pd y intermetallic compounds formed around 250 °C significantly decrease the sensing response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tuning Ligand–Coordinated Single Metal Atoms on TiO 2 and their Dynamic Response during Hydrogenation Catalysis

Ligand-coordinated supported catalysts (LCSCs) are of growing interest for heterogeneous single-atom catalysis. Here, the effect of the choice of organic ligand on the activity and stability of TiO 2 -supported single-atom Pt-ligand catalysts was investigated for ethylene hydrogenation. The activity of these catalysts showed a significant dependence on the choice of ligand and also correlated with coordination number for Pt-ligand and Pt-Cl - . Of the three ligands examined in this study, the one with the lowest Pt coordination number, 1,10-phenanthroline-5,6-dione (PDO), showed the lowest reaction temperature and highest reaction rate, likely due to those metal sites being more accessible to reactant adsorption. In-situ X-ray absorption spectroscopy (XAS) experiments showed that the activity also correlated with good heterolytic dissociation of hydrogen, which was supported by OH/OD exchange experiments and was the rate-determining step of the hydrogenation reaction. In these in-situ XAS experiments up to 190 degrees C, the supported Pt-ligand catalyst showed excellent stability against structural and chemical change. Instead of Pt, the PDO ligand could be coordinated with Ir on TiO 2 to form Ir LCSCs that showed slow activation by loss of Ir-Cl bonds, then excellent stability in the hydrogenation of ethylene. Furthermore, these results provide the chance to engineer ligand-coordinated supported catalysts at the single-atom catalyst level by the choice of ligand and enable new applications at relatively high temperature.

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

Passive NO x adsorption on Pd/H-ZSM-5: Experiments and modeling

A combined experimental and modeling study of the passive NO x adsorber (PNA) is presented that advances the understanding and prediction of the effects of various operating parameters and material properties of H-ZSM-5 and Pd/H-ZSM-5. Experiments reveal the NO x uptake process to be kinetically limited. Two microkinetic schemes are developed to explain the NO x uptake and release and NO 2 generation data. Both schemes are incorporated into a 1+1 D monolith model to predict and validate NO x uptake and temperature programmed desorption (TPD) data. Scheme I involves Z – [PdOH] + , Z – Pd 2+ Z – and Z – Pd + with Z – Pd + as the strongest NO binding site. Scheme II involves reduction of PdO 2 to PdO and nitrate formation. Model tuning utilizes a combination of infrared spectroscopy measurements and density functional theory (DFT) estimates of energy barriers. Lastly, the model is validated at different conditions including feed parameters and Pd loading.

42 ENGINEERING↗
DOE OSTI2022

Effect of framework Al pairing on NO storage properties of Pd-CHA passive NOx adsorbers

For this study, three Pd/H-CHA samples were prepared containing 53.0%, 10.8% and 6.5% paired Al sites at near fixed Si/Al ratio and similar Pd loading. According to H 2 temperature-programmed reduction, Pd was present almost exclusively as isolated cations in the two samples containing the higher concentrations of paired Al sites, whereas in the other sample PdO was also present. Simulated lean cold start tests on the fresh samples conducted in a microflow reactor showed that the sample containing PdO stored the lowest amount of NOx. When tested with CO/H 2 , the sample containing 53.0% paired Al sites showed significantly better storage capacity than the other samples and deactivated less rapidly upon sequential tests. Experiments using lean gasoline engine exhaust revealed similar trends. This study showed that a high concentration of paired Al sites in Pd/H-CHA is beneficial for NOx storage capacity, thermal durability, and minimizing deactivation in the presence of CO/H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Heterogenization of Homogeneous Ruthenium(II) Catalysts for Carbon-Neutral Dehydrogenation of Polyalcohols

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Homogeneous catalysts are promising for the selective and reversible release of hydrogen from LOHC. However, separation from product mixtures and recycling inhibit their use, particularly when comprised of costly low-abundance elements, motivating the development of heterogeneous versions that are more easily recovered and reused. Here, we describe two methods for the heterogenization of molecular Ru catalysts that efficiently dehydrogenate the polyalcohol LOHCs ethylene glycol (EG) and 1,2-propanediol (1,2-PDO). The heterogeneous versions of these catalysts maintain catalytic activity for hydrogen production comparable to the homogeneous complexes, with up to 81% conversion and 99% selectivity. Further, DFT modeling indicates mechanistic similarities for the dehydrogenations of EG and 1,2-PDO, with the rate-limiting steps associated with protonation of the Ru–H bond to form H 2 and the alkoxide species coordinated to Ru(II), followed by β-hydride elimination to regenerate the Ru–H bond. Overall, the data suggest these heterogenized molecular catalysts have potential for practical use in polyalcohol-based LOHC systems.

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

Contrasting Recent and Future ITCZ Changes from Distinct Tropical Warming Patterns

The Intertropical Convergence Zone (ITCZ) is a salient feature of the Earth’s deep-tropical circulation. Here we report and explain the contrasting changes in seasonal ITCZs over recent decades and under future warming. We show that seasonal ITCZs have shifted poleward and narrowed over recent decades but are projected to shift equatorward and widen under future warming. Such contrasting changes are induced by distinct surface warming patterns. Specifically, the equatorial Pacific has cooled over recent decades with phase change in the Pacific Decadal Oscillation (PDO) but in the future it will experience stronger anthropogenic warming than the tropical mean. The effect of surface warming pattern on ITCZ is consistently explained by thermodynamic and energetic theories and is demonstrated through atmosphere-only simulations forced with prescribed SST. In the coming decades, PDO may change into a positive phase. This will enhance the equatorial warming and lead to amplified ITCZ changes that are distinct from recent trends.

Zhou, Wenyu↗
DOE OSTI2023

Pacific decadal oscillation causes fewer near-equatorial cyclones in the North Indian Ocean

Tropical cyclones do not form easily near the equator but can intensify rapidly, leaving little time for preparation. We investigate the number of near-equatorial (originating between 5°N and 11°N) tropical cyclones over the north Indian Ocean during post-monsoon season (October to December) over the past 60 years. The study reveals a marked 43% decline in the number of such cyclones in recent decades (1981–2010) compared to earlier (1951–1980). Here, we show this decline in tropical cyclone frequency is primarily due to the weakened low-level vorticity modulated by the Pacific Decadal Oscillation (PDO) and increased vertical wind shear. In the presence of low-latitude basin-wide warming and a favorable phase of the PDO, both the intensity and frequency of such cyclones are expected to increase. Such dramatic and unique changes in tropical cyclonic activity due to the interplay between natural variability and climate change call for appropriate planning and mitigation strategies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Explaining the trends and variability in the United States tornado records using climate teleconnections and shifts in observational practices

The annual frequency of tornadoes during 1950–2018 across the major tornado-impacted states were examined and modeled using anthropogenic and large-scale climate covariates in a hierarchical Bayesian inference framework. Anthropogenic factors include increases in population density and better detection systems since the mid-1990s. Large-scale climate variables include El Niño Southern Oscillation (ENSO), Southern Oscillation Index (SOI), North Atlantic Oscillation (NAO), Pacific Decadal Oscillation (PDO), Arctic Oscillation (AO), and Atlantic Multi-decadal Oscillation (AMO). The model provides a robust way of estimating the response coefficients by considering pooling of information across groups of states that belong to Tornado Alley, Dixie Alley, and Other States, thereby reducing their uncertainty. The influence of the anthropogenic factors and the large-scale climate variables are modeled in a nested framework to unravel secular trend from cyclical variability. Population density explains the long-term trend in Dixie Alley. The step-increase induced due to the installation of the Doppler Radar systems explains the long-term trend in Tornado Alley. NAO and the interplay between NAO and ENSO explained the interannual to multi-decadal variability in Tornado Alley. PDO and AMO are also contributing to this multi-time scale variability. SOI and AO explain the cyclical variability in Dixie Alley. This improved understanding of the variability and trends in tornadoes should be of immense value to public planners, businesses, and insurance-based risk management agencies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal

Reversibly adjusting the active structures of supported metal catalysts in response to dynamic working conditions has long been pursued. Here we report the reaction-environment-modulated transformations of subnanometre-sized Pd on CeO 2 for efficient methane removal, leveraging the reaction environments at different stages of automotive exhaust aftertreatment. During the cold start of vehicles, inactive Pd 1 single atoms are readily transformed into PdO $x$ subnanometre clusters by CO even at room temperature with excess O 2 , resulting in boosted low-temperature CH 4 oxidation. At elevated temperatures, dispersion of PdO $x$ cluster into Pd 1 against metal sintering renders outstanding hydrothermal stability to the catalyst, to be activated during the next vehicle start. Combined experimental and computational studies elucidate the dynamically evolved Pd speciation on CeO 2 at an atomic level. In conclusion, modulating the reversible nature of supported metals helps overcome the long-existing trade-off between low-temperature activity and high-temperature stability, also providing a new paradigm for designing intelligent catalysts that brings single-atom/cluster catalysts closer to real applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ligand-coordinated Ir single-atom catalysts stabilized on oxide supports for ethylene hydrogenation and their evolution under a reductive atmosphere

In this work, we present a novel series of oxide-supported Ir-ligand single-atom catalysts (SACs) for ethylene hydrogenation. The SACs were created by a metal–ligand self-assembly strategy developed by our group, using one of two ligands, either 1,10-phenanthroline-5,6-dione (PDO) or 3,6-Di-2-pyridyl-1,2,4,5-tetrazine (DPTZ), on powder supports of either CeO 2 or MgO. Characterization by XAS, XPS, and CO adsorption proved that Ir exist principally as highly uniform, cationic single-atoms. Ir SACs show significantly higher durability and metal utilization efficiency than Ir nanoparticle (NP) catalysts during ethylene hydrogenation at 100 °C, as well as excellent stability, as no Ir aggregates were detected after >10 h reaction. The activity can be tuned by ligand and support effects: PDO and CeO 2 are superior to DPTZ and MgO, respectively. This tunability is attributed to differences in H 2 activation capability, which results from differences in support reducibility, electron density on Ir, and, potentially, the local coordination environment of Ir. The Ir SACs lose H 2 activation activity either under inert gas or under H 2 . Through XPS and in situ XAS studies, we attributed the former to the reversible loss of Ir hydride, which is the active species for H 2 activation, and the latter to irreversible over-hydrogenation and loss of Ir–O/N coordination. This work presents a new type of Ir hydrogenation SACs that are more durable, efficient, and tunable than supported Ir NPs, while more stable than homogeneous Ir complexes. It also offers fundamental understanding regarding ligand and support effects, as well as the evolution of Ir single-atoms under H 2 , instructing future design of stable, effective hydrogenation SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrochemical production of H 2 O 2 on palladium-based clusters driven by metal–support interaction

Utilizing palladium (Pd) clusters as active sites offers a promising route to minimize noble metal consumption in electrochemical hydrogen peroxide (H 2 O 2 ) production. In this work, we present a synthesis approach for anchoring Pd-based clusters onto carbon-supported CeO 2 nanosubstrates to enable efficient H 2 O 2 generation via the two-electron oxygen reduction reaction (ORR) pathway. By systematically adjusting Pd loading, we evaluated its impact on H 2 O 2 yield and production rate. The catalyst with the lowest Pd content (0.027 wt%) exhibited outstanding performance, achieving 97% H 2 O 2 selectivity, 94.2 faradaic efficiency at 0.7 V vs. RHE, and a peak production rate of 195.8 mol g Pd −1 h −1 . A formulation containing 0.35 wt% Pd delivered a peak ORR mass activity nearly three times as high as that of commercial 10 wt% Pd/C, while retaining comparable electrochemical stability. These enhancements are attributed to synergistic effects among isolated PdO clusters, CeO 2 nanocrystals, and the conductive carbon support, which together facilitate oxygen adsorption and promote the two-electron ORR pathway. Analysis after accelerated durability testing further revealed a tendency toward cluster agglomeration and mass transfer from smaller to larger nanocrystals, indicative of a coarsening mechanism. Overall, this study underscores the promise of low-Pd PdO–CeO 2 –carbon hybrid catalysts for scalable and efficient H 2 O 2 electrosynthesis, while highlighting stability as a critical area for future improvement.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Representation of Modes of Variability in Six U.S. Climate Models

We compare the performance of several modes of variability across six U.S. climate modeling groups, with a focus on identifying robust improvements in recent models [including those participating in phase 6 of the Coupled Model Intercomparison Project (CMIP)] compared to previous versions. In particular, we examine the representation of the Madden–Julian oscillation (MJO), El Niño–Southern Oscillation (ENSO), the Pacific decadal oscillation (PDO), the quasi-biennial oscillation (QBO) in the tropical stratosphere, and the dominant modes of extratropical variability, including the southern annular mode (SAM), the northern annular mode (NAM) [and the closely related North Atlantic Oscillation (NAO)], and the Pacific–North American pattern (PNA). Where feasible, we explore the processes driving these improvements through the use of “intermediary” experiments that utilize model versions between CMIP3/5 and CMIP6 as well as targeted sensitivity experiments in which individual modeling parameters are altered. We find clear and systematic improvements in the MJO and QBO and in the teleconnection patterns associated with the PDO and ENSO. Some gains arise from better process representation, while others (e.g., the QBO) from higher resolution that allows for a greater range of interactions. Our results demonstrate that the incremental development processes in multiple climate model groups lead to more realistic simulations over time.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Removing the Effects of Tropical Dynamics from North Pacific Climate Variability

Teleconnections from the Tropics energize variations of the North Pacific climate, but detailed diagnosis of this relationship has proven difficult. Simple univariate methods, such as regression on El Niño-Southern Oscillation (ENSO) indices, may be inadequate since the key dynamical processes involved -- including ENSO diversity in the Tropics, re-emergence of mixed layer thermal anomalies, and oceanic Rossby wave propagation in the North Pacific -- have a variety of overlapping spatial and temporal scales. Here we use a multivariate Linear Inverse Model to quantify tropical and extra-tropical multi-scale dynamical contributions to North Pacific variability, in both observations and CMIP6 models. In observations, we find that the Tropics are responsible for almost half of the seasonal variance, and almost three quarters of the decadal variance, along the North American coast and within the subtropical front region northwest of Hawaii. SST anomalies that are generated by local dynamics within the Northeast Pacific have much shorter time scales, consistent with transient weather forcing by Aleutian low anomalies. Variability within the Kuroshio-Oyashio Extension (KOE) region is considerably less impacted by the Tropics, on all time scales. Consequently, without tropical forcing the dominant pattern of North Pacific variability would be a KOE pattern, rather than the Pacific Decadal Oscillation (PDO). In contrast to observations, most CMIP6 historical simulations produce North Pacific variability that maximizes in the KOE region, with amplitude significantly higher than observed. Correspondingly, the simulated North Pacific in all CMIP6 models is shown to be relatively insensitive to the Tropics, with a dominant spatial pattern generally resembling the KOE pattern, not the PDO.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Evolution of the Internal Climate Modes under Future Warming

Abstract Climate modes play an important role in weather and climate variability over multiple spatial and temporal scales. This research assesses Earth system model (ESM) projections of the spatiotemporal characteristics of key internal climate modes (NAM, SAM, PNA, ENSO, PDO, and AMO) under high (SSP585) and low (SSP126) radiative forcing scenarios and contextualizes those projections using historical fidelity. Time series analyses are used to assess trends and mode phase characteristics are summarized for the historical period and for the end of the twenty-first century. Spatial patterns are compared to infer morphological changes. Shifts in the power spectra are used to examine changes in variability at subannual, interannual, and interdecadal scales. Changes in time-lagged correlations are used to capture the evolution of first-order interactions. While differences in historical skill are predominantly ESM dependent, changing mode characteristics in a warmer climate also exhibit variability between individual ensemble realizations. NAM, SAM, and ENSO tend to evolve toward increased prevalence of the positive phase up to 2100 across the multimodel ensemble while the PNA and PDO exhibit little trend but increasing phase intensity. AMO characteristics are shown to depend on the method used to remove the external signal. ESMs that show higher historical fidelity tend to show more modest changes in those modes under global nonstationarity. Changes in mode interactions are found to be highly ESM dependent but exhibit broadly similar behavior to historical relationships. These findings have implications for our understanding of internal variability and make clear that the choice of ESM, and even the ESM realization, matters for applications of climate projections. Significance Statement Internal modes of variability are important to understand due to their impact on local, regional, and global weather and climate patterns. Future climate changes will not only be affected by the variability arising from these modes, but the modes will themselves change in response to the changing climate. Spatial and temporal aspects of the modes are assessed from projections of future climate and related to how well they are captured in the historical climate. This yields some measure of confidence in the changes exhibited by the models. In most cases, when historically skillful models exhibit changes that are different from those produced by less skillful models, they tend to produce more modest changes. These results, as well as the variability between model outcomes, mean decisions on which ESM to use for projections of the future climate matter significantly.

Meteorology & Atmospheric Sciences↗
DOE OSTI2025

Climate models project increasing precipitation in the US Southwest in 2024–2100

We analyzed the measured precipitation in the southwestern US and found that, from 1900 to 2024, precipitation decreased at an average rate of − 1.2 cm per year per 100 years. The most significant precipitation decreases occurred in the three-month period from February to April. At the same time, precipitation during the southwestern monsoon season (July, August, and September) remained relatively stable. The ensemble mean of all CMIP6 (Coupled Model Intercomparison Project phase 6) climate models, along with the regression model incorporating anthropogenic aerosol (AER) and Pacific Decadal Oscillation (PDO) as predictors, projects precipitation to increase from 2024 to 2100. This projected precipitation increase relies on the anticipated decrease in emissions of anthropogenic aerosols, which is associated with the transition from fossil fuel burning to renewable and nuclear energy sources.

54 ENVIRONMENTAL SCIENCES↗