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Stereochemical expression of Bi 6s 2 lone pairs mediates fluoride-ion (De)insertion in tunnel-structured Bi 2 PdO 4 and Bi 1.6 Pb 0.4 PtO 4
An energy storage concept using anions as charge carriers is explored based on solution-phase fluoride-ion insertion in periodic solids. Redox reactions are mediated by d-block centers, whereas Bi 3+ lone pairs enable reversible F-ion diffusion.
Replication Data for: Reduction of Oxidized Pd/Ag(111) Surfaces by H2: Sensitivity to PdO Island Size and Dispersion
The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573.
Transition metal oxides - CrO, MoO, NiO, PdO, AgO
The transition-metal oxides are quite ionic; Mulliken population analyses for several oxides give a negative charge of about 0.7 electrons for oxygen. When the transition-metal d shell is only partially filled, the orbitals are involved in covalent bonds with O; both two-electron bonding (2)-antibonding (0) and one-electron bonding (2)-antibonding (1) bonds are formed. These covalent bonds occur in addition to the ionic bonding. There is d-sigma-O2 p sigma repulsion, and this repulsion is reduced when the d-sigma electron is promoted into an orbital which has dominantly 4sp-sigma character and is polarized away from O.
Indian monsoon's relation with the decadal part of PDO in observations and NCAR CCSM4
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Pacific decadal oscillation remotely forced by the equatorial Pacific and the Atlantic Oceans
Abstract The Pacific Decadal Oscillation (PDO), the leading mode of Pacific decadal sea surface temperature variability, arises mainly from combinations of regional air-sea interaction within the North Pacific Ocean and remote forcing, such as from the tropical Pacific and the Atlantic. Because of such a combination of mechanisms, a question remains as to how much PDO variability originates from these regions. To better understand PDO variability, the equatorial Pacific and the Atlantic impacts on the PDO are examined using several 3-dimensional partial ocean data assimilation experiments conducted with two global climate models: the CESM1.0 and MIROC3.2m. In these partial assimilation experiments, the climate models are constrained by observed temperature and salinity anomalies, one solely in the Atlantic basin and the other solely in the equatorial Pacific basin, but are allowed to evolve freely in other regions. These experiments demonstrate that, in addition to the tropical Pacific’s role in driving PDO variability, the Atlantic can affect PDO variability by modulating the tropical Pacific climate through two proposed processes. One is the equatorial pathway, in which tropical Atlantic sea surface temperature (SST) variability causes an El Niño-like SST response in the equatorial Pacific through the reorganization of the global Walker circulation. The other is the north tropical pathway, where low-frequency SST variability associated with the Atlantic Multidecadal Oscillation induces a Matsuno-Gill type atmospheric response in the tropical Atlantic-Pacific sectors north of the equator. These results provide a quantitative assessment suggesting that 12–29% of PDO variance originates from the Atlantic Ocean and 40–44% from the tropical Pacific. The remaining 27–48% of the variance is inferred to arise from other processes such as regional ocean-atmosphere interactions in the North Pacific and possibly teleconnections from the Indian Ocean.
Carboxylic acid ligand substituent impacts hydrosilylation activity of platinum single atom catalysts on ceria
Current industrially employed hydrosilylation catalysts rely on homogeneous platinum catalysts which are not recovered after the reaction. To eliminate this issue, our group has been working to optimize recyclability of heterogeneous platinum single atom catalysts (SACs) on ceria via 1,10-phenanthroline-5,6-dione ligands (PDO), which incorporates mono (PDO-C) and dicarboxylic acid (PDO-C2) groups in the 2- and 9-position of PDO ligand to increase metal–surface interaction. DRIFTS results confirm carboxylic acid coordination to the terminal hydroxy groups of the ceria surface. New catalyst synthesis conditions wherein PDO was combined with the metal prior to exposure to the surface allow control of Pt oxidation state on the surface. Here, the highest metal loading was observed for PDO and PDO-C, correlating with improved catalytic recyclability compared to the PDO-C2 ligand. It is proposed that the location of the carboxylic acid groups and the steric effects can explain the lower activity and metal loading for PDO-C2 ligands. Post-reaction XPS and DRIFTS spectra show the appearance of new Si and O species on the catalyst during the hydrosilylation reaction, indicating the silane reagent is depositing on the surface. The silane coverage and leaching of catalyst from the surface is the cause for the reduced catalytic activity.
Modulation of ENSO teleconnections over North America by the Pacific decadal oscillation
In this study, we investigate whether the Pacific decadal oscillation (PDO) can enhance or diminish El Niño Southern Oscillation (ENSO) temperature and precipitation teleconnections over North America using five single model initial-condition large ensembles (SMILEs). The use of SMILEs facilitates a statistically robust comparison of ENSO events that occur during different phases of the PDO. We find that a positive PDO enhances winter and spring El Niño temperature and precipitation teleconnections and diminishes La Niña teleconnections. A negative PDO has the opposite effect. The modulation of ENSO by the PDO is mediated by differences in the location and strength of the Aleutian Low and Pacific Jet during ENSO events under different phases of the PDO. This modulation is a simple combination of the individual effects of the PDO and ENSO over North America. Finally, we show that ENSO and the PDO can be used to evaluate the likelihood of the occurrence of temperature and precipitation anomalies in different regions, but cannot be used as a deterministic predictor of these anomalies due to the large variability between individual events.
High-level co-production of 3-hydroxypropionic acid and 1,3-propanediol from glycerol: Metabolic engineering and process optimization
3-Hydroxypropionic acid (3-HP) and 1,3-propanediol (1,3-PDO) are value-added chemicals with versatile applications in the chemical, pharmaceutical, and food industries. Nevertheless, sustainable production of 3-HP and 1,3-PDO is often limited by the lack of efficient strains and suitable fermentation configurations. We report attempts have been made to improve the co-production of both metabolites through metabolic engineering of Escherichia coli and process optimization. First, the 3-HP and 1,3-PDO co-biosynthetic pathways were recruited and optimized in E. coli, followed by coupling the pathways to the transhydrogenase-mediated cofactor regeneration systems that increased cofactor availability and product synthesis. Next, pathway rebalancing and block of by-product formation significantly improved 3-HP and 1,3-PDO net titer. Subsequently, glycerol flux toward 3-HP and 1,3-PDO synthesis was maximized by removing metabolic repression and fine-tuning the glycerol oxidation pathway. Lastly, the combined fermentation process optimization and two-stage pH-controlled fed-batch fermentation co-produced 140.50 g/L 3-HP and 1,3-PDO, with 0.85 mol/mol net yield.
North Pacific Decadal Variability in the GEOS-5 Atmosphere-Ocean Model
This study examines the mechanisms of the Pacific decadal oscillation (PDO) in the GEOS-5 general circulation model. The model simulates a realistic PDO pattern that is resolved as the first empirical orthogonal function (EOF) of winter sea surface temperature (SST). The simulated PDO is primarily forced by Aleutian low through Ekman transport and surface fluxes, and shows a red spectrum without any preferred periodicity. This differs from the observations, which indicate a greater role of El Nino-Southern Oscillation (ENSO) forcing, and likely reflects the too short time scale of the simulated ENSO. The geostrophic transport in response to the Aleutian low is limited to the Kuroshio-Oyashio Extension, and is unlikely the main controlling factor in this model, although it reinforces the Ekman-induced SST anomalies. The delay between the Aleutian low and the PDO is relatively short (1 year) suggesting that the fast Ekman response (rather than Rossby wave propagation) sets the SST pattern immediately following an Aleutian low fluctuation. The atmospheric feedback (response to the SST) is only about 25 of the forcing and never evolves into an Aleutian low completely, instead projecting onto the North Pacific Oscillation (NPO), a meridional dipole in sea level pressure (SLP). The lack of preferred periodicity and weak atmospheric response bothindicate a coupled oscillation is an unlikely mechanism for the PDO in this model. In agreement with recent studies, the NPO is correlated with the North Pacific Gyre Oscillation (NPGO), which is another leading EOF of the North Pacific SST. A possible connection between the PDO and the NPGO is discussed.
Insights into palladium poisoning of Cu/SSZ-13 selective catalytic reduction catalysts
Here, the impacts of Pd poisoning to the activity, selectivity, and hydrothermal stability of Cu/SSZ-13 selective catalytic reduction (SCR) catalysts are reported. Pd lowers DeNOx efficiency of Cu/SSZ-13 via two mechanisms: (1) displacing SCR active sites in the form of isolated Pd-ions, and (2) catalyzing non-selective NH 3 oxidation in the form of PdO. The first mechanism works by the diffusion of isolated Pd-ions into chabazite cages to displace ZCu II OH SCR active species, and it occurs on Cu/SSZ-13 catalysts with and without external surface CuO clusters in similar fashion. In contrast, the second mechanism works differently with and without external surface CuO clusters. For Cu/SSZ-13 catalyst without external CuO clusters (i.e., primarily isolated Cu-ions), PdO leads to significant decrease of DeNOx efficiency at reaction temperatures above ~400°C due to its non-selective NH 3 oxidation activity at high temperatures. However, this poisoning effect becomes much less impactful on Cu/SSZ-13 catalyst containing CuO clusters. This is due to the formation of CuO-PdO solid solution via interactions between CuO and PdO, which reduces non-selective NH 3 oxidation potential. Furthermore, this solid solution formation even mitigates adverse effects caused by hydrothermal aging. Hence, the poisoning effects of Pd are closely related to Cu speciation and spatial distribution of a Cu/SSZ-13 catalyst. Finally, this study suggests a strategy in eliminating Pd poisoning, that is, the introduction of an oxide phase that effectively traps PdO but does not adversely influence SCR.
Reaction nanoscopy of ion emission from sub-wavelength propanediol droplets
Abstract Droplets provide unique opportunities for the investigation of laser-induced surface chemistry. Chemical reactions on the surface of charged droplets are ubiquitous in nature and can provide critical insight into more efficient processes for industrial chemical production. Here, we demonstrate the application of the reaction nanoscopy technique to strong-field ionized nanodroplets of propanediol (PDO). The technique’s sensitivity to the near-field around the droplet allows for the in-situ characterization of the average droplet size and charge. The use of ultrashort laser pulses enables control of the amount of surface charge by the laser intensity. Moreover, we demonstrate the surface chemical sensitivity of reaction nanoscopy by comparing droplets of the isomers 1,2-PDO and 1,3-PDO in their ion emission and fragmentation channels. Referencing the ion yields to gas-phase data, we find an enhanced production of methyl cations from droplets of the 1,2-PDO isomer. Density functional theory simulations support that this enhancement is due to the alignment of 1,2-PDO molecules on the surface. The results pave the way towards spatio-temporal observations of charge dynamics and surface reactions on droplets.
Influences of the El Nino Southern Oscillation and the Pacific Decadal Oscillation on the Timing of the North American Spring
Detrended, modelled first leaf dates for 856 sites across North America for the period 1900-2008 are used to examine how the El Nino Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO) separately and together might influence the timing of spring. Although spring (mean March through April) ENSO and PDO signals are apparent in first leaf dates, the signals are not statistically significant (at a 95% confidence level (p <0.05)) for most sites. The most significant ENSO/PDO signal in first leaf dates occurs for El Nino and positive PDO conditions. An analysis of the spatial distributions of first leaf dates for separate and combined ENSO/PDO conditions features a northwest-southeast dipole that is significantly (at p <0.05) different than the distributions for neutral conditions. The nature of the teleconnection between Pacific SST's and first leaf dates is evident in comparable composites for detrended sea level pressure (SLP) in the spring months. During positive ENSO/PDO, there is an anomalous flow of warm air from the southwestern US into the northwestern US and an anomalous northeasterly flow of cold air from polar regions into the eastern and southeastern US. These flow patterns are reversed during negative ENSO/PDO. Although the magnitudes of first leaf date departures are not necessarily significantly related to ENSO and PDO, the spatial patterns of departures are significantly related to ENSO and PDO. These significant relations and the long-lived persistence of SSTs provide a potential tool for forecasting the tendencies for first leaf dates to be early or late.
North Pacific Decadal Variability: Insights from a Biennial ENSO Environment
This study examines the mechanisms of the Pacific decadal oscillation (PDO) in the NASA GEOS-5 general circulation model (GCM). Similar to several other state-of-the-art GCMs, the El Niño-Southern Oscillation (ENSO) simulated by the GEOS-5 has a strong biennial periodicity. Since this is a model bias that precludes a strong role of ENSO, it provides a unique environment to assess the other leading mechanisms of North Pacific decadal variability. Despite the biennial ENSO periodicity, the model simulates a realistic PDO pattern in the North Pacific that is resolved as the first empirical orthogonal function (EOF) of winter mean sea surface temperature (SST). The spectrum of the PDO indicates no preferred periodicity. The SST anomalies associated with the PDO, particularly its basin wide structure, are primarily forced by the Aleutian low through Ekman transport. The slow geostrophic transport in association with the meridional adjustment of the subtropical gyre is limited to a narrow region in the Kuroshio-Oyashio extension, north of 40degN. The atmosphere's response to the PDO, while weak, projects onto the North Pacific Oscillation (NPO), a meridional dipole in sea level pressure. Both the lack of preferred periodicity and the weak atmospheric response indicate an air-sea coupled oscillation is an unlikely mechanism in this model. In agreement with recent studies, the NPO is correlated with the North Pacific Gyre Oscillation, which is another leading EOF of North Pacific SST variability. The results emphasize the role of atmospheric variability in the North Pacific SST modes, thereby bringing into question the potential for their predictability.
Long-Term Changes/Trends in Surface Temperature and Precipitation During the Satellite Era (1979-2012)
During the post-1979 period in which the satellite-based precipitation measurements with global coverage are available, global mean surface temperature rapidly increased up to late 1990s, followed by a period of temperature hiatus after about 19981999. Comparing observed surface temperature trends against the simulated ones by the CMIP5 historical experiments especially in the zonal mean context suggests that although the anthropogenic greenhouse-gases (GHG) forcing has played a major role, in addition to the anthropogenic aerosols and various natural forcings, the effects from decadal-to-interdecadal scale internal modes specifically the Pacific Decadal Oscillation(PDO) are also very strong. Evident temperature changes associated with the PDOs phase shift are seen in the Pacific basin, with decadal-scale cooling in the tropical central-eastern Pacific and most of the east basin and concurrent warming in the subtropics of both hemispheres,even though the PDOs net effect on global mean temperature is relatively weak. The Atlantic Multidecadal Oscillation(AMO) also changed its phase in the mid-1990s, and hence its possible impact is estimated and assessed as well.However, comparisons with CMIP5 simulations suggest that the AMO may have not contributed as significantly as the PDO in terms of the changes trends in global surface temperature, even though the data analysis technique used here suggests otherwise. Long-term precipitation changes or trends during the post-1979 period are further shown to have been modulated by the two major factors:anthropogenic GHG and PDO, in addition to the relatively weak effects from aerosols and natural forcings. The spatial patterns of observed precipitation trends in the Pacific,including reductions in the tropical central-eastern Pacific and increases in the tropical western Pacific and along the South Pacific Convergence Zone, manifest the PDOs contributions.Removing the PDO effect from the total precipitation trends makes the spatial structures of precipitation trends more similar to those simulated by CMIP5 historical full forcing experiments particularly in the context of zonal-mean results. This also confirms that in spite of the PDO effect specifically on regional scales, the anthropogenic GHG signals are still discernible in observed precipitation during the time period. Following the increase of GHG, precipitation tends to increase roughly along the climatological ITCZ and decrease south of the equator and in the subtropics of both hemispheres.
Palladium/Zeolite Low Temperature Passive NOx Adsorbers (PNA): Structure-Adsorption Property Relationships for Hydrothermally Aged PNA Materials
Zeolites with different framework structures (SSZ-13, ZSM-5, BEA) but similar Si/Al ratios and Pd loading (~1 wr%) were synthesized and evaluated as low temperature passive NOx adsorbers (PNA). These materials exhibit high NOx adsorption efficiency with atomically dispersed Pd the active adsorption site. Hydrothermal aging at 750 ºC for 16 hours in the presence of 10% water vapor in air resulted in the formation of PdO nanoparticles in all three samples as evidenced by high energy XRD. Hydrothermal aging of the small-pore Pd/SSZ-13 (Si/Al = 6), which contain ~100-90% atomically dispersed palladium ions, decreases its PNA performance only by ~10-20%. High-field solid state 27Al NMR studies on the fresh and aged samples substantiate dealumination and significant changes in the distribution of Al (and thus, Bronsted acid) sites after hydrothermal aging. FTIR measurements with NO probe molecule and titration of Bronsted acid sites with nitrosyl (NO+) ions further corroborate the 27Al NMR data. Because framework aluminum atoms are the anchoring sites for atomically dispersed Pd ions, their elution from the framework causes the loss of active atomically dispersed Pd species. Furthermore, with the aid of HAADF-STEM imaging and synchrotron XRD studies, we further confirm and visualize the fate of these Pd species – they agglomerate into PdO nanoparticles on the external surface of zeolite. Consequently, these changes lead to the decrease in PNA performance of these materials after hydrothermal aging. The thus formed agglomerates cannot be re-dispersed back to their ionic state due to the loss of framework Al T-sites and/or inherent stability of such large PdO particles. Our study clearly demonstrates that, unlike in previous studies that found increased PNA performance upon HTA , high temperatures hydrothermal aging of PNA materials that contain atomically dispersed Pd initially, results in a decrease in NOx storage efficiency due mostly to the formation of PdO agglomerates. However, we also highlight the high hydrothermal stability of predominantly atomically dispersed 1-3 wt% Pd/SSZ-13 (Si/Al = 6), whose performance decreases only marginally after prolonged hydrothermal aging at 750 ºC. Overall, this study shows that hydrothermally stable passive NOx materials can be prepared using small-pore SSZ-13 zeolite.
Recent Accelerated Decadal Shift in Winter North American Temperature Patterns Under Pacific‐Atlantic Decadal Variability
Global warming and internal climate variability have changed winter temperature extreme regimes in North America, affecting droughts and wildfires in the western United States. However, how internal climate variability influences North American winter temperature extreme patterns remains poorly understood. Here, we demonstrate that the recent winter North American surface air temperature (SAT) exhibits an accelerated decadal alternation between Warm West-Cold East (WWCE) and Cold West-Warm East (CWWE) dipoles because their variations show shorter decadal periods during 1990–2022 than during 1950–1989 and are regulated by the Pacific Decadal Oscillation (PDO) variability. While the winter WWCE dipole mainly linked to North Pacific blocking events exhibited a smaller mean amplitude during 1990–2022 than 1950–1989 due to the weakened positive PDO phase during 1990–2022 under the positive phase of the Atlantic Multidecadal Oscillation (AMO), the winter CWWE showed a larger mean amplitude during 1990–2022 due to the stronger negative PDO phase than during 1950–1989. Our results further suggest that the recent rapid decadal shift of North American winter temperatures is primarily attributed to the PDO variability likely due to anthropogenic warming under the positive AMO.
DFO Computational Modeling Project - Catalytic Upgrading of Bio-based Furfural to 1,5-Pentanediol: A New Renewable Monomer for the Coatings Industry (Final Report)
This report summarizes the results of a collaborative effort between Oak Ridge National Laboratory (ORNL) and Pyran™ Inc. to utilize modeling capabilities developed by the CCPC (Consortium for Computational Physics and Chemistry) to assist Pyran in scaling up its proprietary process for thermocatalytic conversion of furfural to 1,5 pentanediol (PDO). Pyran’s bio-based PDO is a direct replacement for petroleum-based PDO and 1,6 hexanediol (HDO) currently used in polymers, additives, coatings, adhesives and sealants. The current market is in excess of $\$$1B/yr. According to Pyran, their production process results in 95+% reduction in fossil CO 2 at lower production costs compared to the existing petroleum-based routes for PDO & HDO. Other chemicals based on intermediates from this process have current markets in excess of $\$$10B/yr.