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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Above-ground net primary productivity in regenerating seasonally dry tropical forest: Contributions of rainfall, forest age and soil

Identifying factors controlling forest productivity is critical to understanding forest-climate change feedbacks, modelling vegetation dynamics and carbon finance schemes. However, little research has focused on productivity in regenerating tropical forests which are expanding in their fraction of global area have an order of magnitude larger carbon uptake rates relative to older forest. Here We examined above-ground net primary productivity (ANPP) and its components (wood production and litterfall) over 10 years in forest plots that vary in successional age, soil characteristics and species composition using band dendrometers and litterfall traps in regenerating seasonally dry tropical forests in northwestern Costa Rica. We show that the components of ANPP are differentially driven by age and annual rainfall and that local soil variation is important. Total ANPP was explained by a combination of age, annual rainfall and soil variation. Wood production comprised 35% of ANPP on average across sites and years, and was explained by annual rainfall but not forest age. Conversely, litterfall increased with forest age and soil fertility yet was not affected by annual rainfall. In this region, edaphic variability is highly correlated with plant community composition. Thus, variation in ecosystem processes explained by soil may also be partially explained by species composition. These results suggest that future changes in annual rainfall can alter the secondary forest carbon sink, but this effect will be buffered by the litterfall flux which varies little among years. In determining the long-term strength of the secondary forest carbon sink, both rainfall and forest age will be critical variables to track. We also conclude that detailed understanding of local site variation in soils and plant community may be required to accurately predict the impact of changing rainfall on forest carbon uptake. Synthesis. We show that in seasonally dry tropical forest, annual rainfall has a positive relationship with the growth of above-ground woody tissues of trees and that droughts lead to significant reductions in above-ground productivity. These results provide evidence for climate change—carbon cycle feedbacks in the seasonal tropics and highlight the value of longitudinal data on forest regeneration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Aridity and forest age mediate landscape scale patterns of tropical forest resistance to cyclonic storms

Abstract Cyclonic storms, or hurricanes, are expected to intensify as ocean heat energy rises due to climate change. Ecological theory suggests that tropical forest resistance to hurricanes should increase with forest age and wood density. However, most data on hurricane effects on tropical forests come from a limited number of well‐studied long‐term monitoring sites, restricting our capacity to evaluate the resistance of tropical forests to hurricanes across broad environmental gradients. In this study, we assessed whether forest age and aridity mediate the effects of hurricanes Irma and Maria in Puerto Rico, Vieques and Culebra islands. We leveraged functional trait data for 410 tree species, remotely sensed measurements of canopy height and cover, along with data on forest stand characteristics of 180 of 338 forest monitoring plots, each covering an area of 0.067 ha. The plots represent a broad mean annual precipitation (MAP) gradient from 701 to 4598 mm and a complex mosaic of forest age from 5 to around 85 years since deforestation. Hurricanes resulted in a 25% increase in basal area mortality rates, a 45% decrease in canopy height and a 21% reduction in canopy cover. These effects intensified with forest age, even after considering proximity to the hurricane path. The links between forest age and hurricane disturbances were likely due the prevalence of tall canopies. Tall forest canopies were strongly linked with low community‐weighted wood density (WD). These characteristics were on average more common in moist and wet forests (MAP >1250 mm). Conversely, dry forests were dominated by short species with high wood density (WD > 0.6 g cm −3 ) and did not show significant increases in basal area mortality rates after the hurricanes. Synthesis . Our findings show that selection towards drought‐tolerant traits across aridity gradients, such as short stature and dense wood, enhances resistance to hurricanes. However, forest age modulated responses to hurricanes, with older forests being less resistant across the islands. This evidence highlights the importance of considering the intricate links between ecological succession and plant function when forecasting tropical forests’ responses to increasingly strong hurricanes.

Vargas G., German↗
DOE OSTI2020

Forest responses to simulated elevated CO 2 under alternate hypotheses of size- and age-dependent mortality

Elevated atmospheric carbon dioxide (eCO 2 ) is predicted to increase growth rates of forest trees. The extent to which increased growth translates to changes in biomass is dependent on the turnover time of the carbon, and thus tree mortality rates. Size- or age-dependent mortality combined with increased growth rates could result in either decreased carbon turnover from a speeding up of tree life cycles, or increased biomass from trees reaching larger sizes, respectively. However, most vegetation models currently lack any representation of size- or age-dependent mortality and the effect of eCO 2 on changes in biomass and carbon turnover times is thus a major source of uncertainty in predictions of future vegetation dynamics. Using a reduced-complexity form of the vegetation demographic model the Functionally Assembled Terrestrial Ecosystem Simulator to simulate an idealised tropical forest, we find increases in biomass despite reductions in carbon turnover time in both size- and age-dependent mortality scenarios in response to a hypothetical eCO 2 -driven 25% increase in woody net primary productivity (wNPP). Carbon turnover times decreased by 9.6% in size-dependent mortality scenarios due to a speeding up of tree life cycles, but also by 2.0% when mortality was age-dependent, as larger crowns led to increased light competition. Increases in aboveground biomass (AGB) were much larger when mortality was age-dependent (24.3%) compared with size-dependent (13.4%) as trees reached larger sizes before death. In simulations with a constant background mortality rate, carbon turnover time decreased by 2.1% and AGB increased by 24.0%, however, absolute values of AGB and carbon turnover were higher than in either size- or age-dependent mortality scenario. The extent to which AGB increases and carbon turnover decreases will thus depend on the mechanisms of large tree mortality: if increased size itself results in elevated mortality rates, then this could reduce by about half the increase in AGB relative to the increase in wNPP.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

The Past, Present and Future of Structural Health Monitoring: An Overview of Three Ages

This paper presents an overview of the discipline of structural health monitoring (SHM), organised in terms of three proposed ages. The first age is delineated by the prehistory of SHM and the period where nondestructing testing methods evolved into an organised set of principles built upon physics-based models; this age ended when the model-based approaches reached an impasse in terms of their ability to properly deal with real-world problems. The second age of SHM began with a transition to data-based methods based on statistical pattern recognition, which provided a holistic approach to SHM problems for the first time. This age arguably ended when the methods foundered in situations where the necessary training data were scarce. It is argued here that the third age began with the development of population-based SHM, which has been designed to overcome the problem of data scarcity. As there is very limited space in a single article to provide a comprehensive overview, an appendix has been provided here that gives a very systematic bibliography of SHM reviews—a meta-bibliography.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Effect of Dual Environment Aging on Flexible Polyurethane Based Adhesive

Abstract Environmental degradation of adhesives naturally increases with the intensity of the ambient weathering agents involved. During service life, these materials are never subjected to a constant environmental loading. Real-time applications expose the material to multiple weather conditions, ranging from dry to humid or fully wet conditions. While some understanding exists about aging environments in isolation, we intend to investigate the effect of multiple environments on the constitutive behavior of the materials in question. The extent of damage can be accessed by analyzing the changes in constitutive behavior and toughness of aged material. Therefore, this aging experiment was designed around two-way aging regimes involving combinations of thermo-oxidation, hydrolytic and hygrothermal aging environments. We selected a polyurethane based flexible adhesive which is commonly used in the automotive industry as a glass sealant. The aged specimens were subjected to uniaxial tensile tests, and variation in material toughness and constitutive behavior was analyzed to ascertain the mechanics involved in the case of each environmental exposure. We outlined how different environments affect the material in isolation and how they interact with other weathering conditions. This study will help better understand and model the damage mechanics involved in exposure to multiple environmental conditions.

Shaafaey, Mamoon↗
DOE OSTI2025

Chromosome duplication causes premature aging via defects in ribosome quality control

Down syndrome, caused by an extra copy of Chromosome 21, causes lifelong problems. One of the most common phenotypes among people with Down syndrome is premature aging, including early tissue decline, neurodegeneration, and shortened life span. Yet the reasons for premature systemic aging are a mystery and difficult to study in humans. Here we show that chromosome amplification in wild yeast also produces premature aging and shortens life span. Chromosome duplication disrupts nutrient-induced cell-cycle arrest, entry into quiescence, and cellular health during chronological aging, across genetic background and independent of which chromosome is amplified. Using a genomic screen, we discovered that these defects are due in part to aneuploidy-induced dysfunction in Ribosome Quality Control (RQC). We show that aneuploids entering quiescence display aberrant ribosome profiles, accumulate RQC intermediates, and harbor an increased load of protein aggregates compared to euploid cells. Although they maintain proteasome activity, aneuploids also show signs of ubiquitin dysregulation and sequestration into foci. Remarkably, inducing ribosome stalling in euploids produces similar aging phenotypes, while up-regulating limiting RQC subunits or poly-ubiquitin alleviates many of the aneuploid defects. We propose that the increased translational load caused by having too many mRNAs accelerates a decline in translational fidelity, contributing to premature aging.

Aneuploidy↗
DOE OSTI2024

Associations between regional blood-brain barrier permeability, aging, and Alzheimer’s disease biomarkers in cognitively normal older adults

Background Increased blood-brain barrier permeability (BBBp) has been hypothesized as a feature of aging that may lead to the development of Alzheimer’s disease (AD). We sought to identify the brain regions most vulnerable to greater BBBp during aging and examine their regional relationship with neuroimaging biomarkers of AD. Methods We studied 31 cognitively normal older adults (OA) and 10 young adults (YA) from the Berkeley Aging Cohort Study (BACS). Both OA and YA received dynamic contrast-enhanced MRI (DCE-MRI) to quantify K trans values, as a measure of BBBp, in 37 brain regions across the cortex. The OA also received Pittsburgh compound B (PiB)-PET to create distribution volume ratios (DVR) images and flortaucipir (FTP)- PET to create partial volume corrected standardized uptake volume ratios (SUVR) images. Repeated measures ANOVA assessed the brain regions where OA showed greater BBBp than YA. In OA, K trans values were compared based on sex, Aβ positivity status, and APOE4carrier status within a composite region across the areas susceptible to aging. We used linear models and sparse canonical correlation analysis (SCCA) to examine the relationship between K trans and AD biomarkers. Results OA showed greater BBBp than YA predominately in the temporal lobe, with some involvement of parietal, occipital and frontal lobes. Within an averaged ROI of affected regions, there was no difference in K trans values based on sex or Aβ positivity, but OA who were APOE4carriers had significantly higher K trans values. There was no direct relationship between averaged K trans and global Aβ pathology, but there was a trend for an Ab status by tau interaction on K trans in this region. SCCA showed increased K trans was associated with increased PiB DVR, mainly in temporal and parietal brain regions. There was not a significant relationship between K trans and FTP SUVR. Discussion Our findings indicate that the BBB shows regional vulnerability during normal aging that overlaps considerably with the pattern of AD pathology. Greater BBBp in brain regions affected in aging is related to APOE genotype and may also be related to the pathological accumulation of Aβ.

Science & Technology - Other Topics↗
DOE OSTI2021

SR19021 Tritium Aging of Regenerated LANA.75 (Final Project Report)

The Savannah River Tritium Enterprise (SRTE) has used the metal hydride LaNi 4.25 Al 0.75 (LANA.75) in the Tritium Facilities for over two decades. LANA.75 beds store significant quantities of tritium but have a limited service life due to the radiolytic decay of tritium to He-3 within the metal matrix. It has been shown that heating tritium-aged LANA.75 under vacuum can reverse tritium aging effects, eliminating the heel of trapped hydrogen, and restoring the reversible capacity. Additional investigation is needed to ensure there are no unexpected changes to the hydride before this restoration technique is employed in full scale beds in the Tritium Facilities. This project was to be comprised of three distinct scopes: obtain tritium aging data on the sample regenerated in 2018, regenerate a tritium-aged sample at 600 °C, and perform thermal stability testing on a non-tritiated sample. Isotherms were collected on the previously regenerated sample after approximately two years of tritium aging. Isotherms were collected at 80, 100, and 120 °C. As expected, there was a decrease in the plateau pressure, an increase in plateau slope, and a portion of the “heel” of tritium trapped in the metal had been reestablished. Unexpectedly, it appeared that the plateau had shortened at the higher tritium to metal ratios as well. This is typically seen in older samples. The second scope, to regenerate a second tritium-aged LANA.75 sample, was not completed. A Task Technical and Quality Assurance Plan was written and approved, a high temperature test cell was fabricated, several pre-job briefs were held, and the hydride sample was passivated with air. Despite these successes, the hydride sample was not recovered from the legacy test cell. The third scope was to perform thermal stability testing on a “cold” LANA.75 sample. A non-tritiated sample of LANA.75 was held at 750 °C under vacuum for 200 hours to simulate exposure to multiple regeneration evolutions. Hydride isotherm performance, chemical composition, crystallinity, particle size, and morphology are compared between the pre- and post-regeneration samples. No significant changes were observed in composition, crystallinity, or particle size. Comparison of before and after isotherms showed that performance improved rather than deteriorated during the evolution. Scanning Electron Microscopy (SEM) analysis showed small growths on the particle surface after exposure to regeneration conditions. Additional testing will be required to determine the cause of these growths.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2022

Effect of thermal aging on microstructure and crack growth response of Alloy 152 weld

Nickel-based Alloy 690 and the associated weld Alloys 52 and 152 are typically used for nozzle penetrations in replacement heads for pressurized water reactor (PWR) vessels, because of their excellent overall resistance to general corrosion and environmental degradation, primarily stress corrosion cracking (SCC). However, many of the existing PWRs are expected to operate for 40-80 years. Likewise, advanced water-cooled small modular reactors (SMRs) will use Ni-Cr alloys and are expected to receive initial operating licenses for 60 years. Hence, the thermal stability of Ni-Cr alloys is a potential concern for the long-term performance of both existing and advanced nuclear power plants, and possibly spent fuel storage containers. The objective of this research is to understand the microstructural changes occurring in high-Cr, Ni-based Alloy 152 weldments during long time exposure to the reactor operating temperatures, and the effect of these changes on the service performance. One area of particular concern is the potential for long range ordering (LRO), i.e. formation of the intermetallic Ni2Cr phase under prolonged exposure to reactor temperatures and/or irradiation, which can increase strength, decrease ductility, and cause dimensional changes or lead to in-service embrittlement of components made with these alloys. Hence, this research focused on the microstructural evolution and the SCC response of Alloy 152 under accelerated thermal aging. The materials studied involved three heats of Alloy 152 used to produce a dissimilar metal weld (DMW) joining an Alloy 690 plate to an Alloy 533 low alloy steel (LAS) plate, thermally aged at three different temperatures (370°C, 400°C and 450°C) for up to 75,000h (equivalent to 60 years of service). The microstructural characterization by means of synchrotron X-ray did not find evidence of LRO in any of the three heats aged to an equivalent of 60 years of service. Testing in a primary water environment of a heat of Alloy 152 aged at 370°C to a 60-year service equivalent revealed a fatigue and corrosion fatigue crack growth responses similar to those measured on the un-aged alloy. However, the SCC CGR response of the aged sample appears to show a deterioration in performance.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Effect of thermal aging on microstructure and stress corrosion cracking behavior of Alloy 152 weldment

Nickel-based Alloy 690 and the associated weld Alloys 52 and 152 are typically used for nozzle penetrations in replacement heads for pressurized water reactor (PWR) vessels, because of their excellent overall resistance to general corrosion and environmental degradation, primarily stress corrosion cracking (SCC). However, many of the existing PWRs are expected to operate for 40-80 years. Likewise, water-cooled small modular reactors (SMRs) will use Ni-Cr alloys and are expected to receive initial operating licenses for 60 years. Hence, the thermal stability of Ni-Cr alloys is a potential concern for the long-term performance of both existing and advanced nuclear power plants, and possibly spent fuel storage containers. The objective of this research is to understand the microstructural changes occurring in high-Cr, Ni-based Alloy 152 weldments during long time exposure to the reactor operating temperatures, and the effect of these changes on the service performance. One area of particular concern is the potential for long range ordering (LRO), i.e. formation of the intermetallic Ni2Cr phase under prolonged exposure to reactor temperatures and/or irradiation, which can increase strength, decrease ductility, and cause dimensional changes or lead to in-service embrittlement of components made with these alloys. Hence, this research focused on the microstructural evolution and the SCC response of Alloy 152 under accelerated thermal aging. The materials studied involved three heats of Alloy 152 used to produce a dissimilar metal weld (DMW) joining an Alloy 690 plate to an Alloy 533 low alloy steel (LAS) plate, thermally aged at three different temperatures (370°C, 400°C and 450°C) for up to 75,000h (equivalent to 60 years of service). The microstructural characterization by means of synchrotron X-ray conducted in small, 0.2 mm - step line scans in the high-deformation regions of the weld root – covering areas spanning from the weld heat affected zone (HAZ) in Alloy 690 to the weld and weld butter on LAS - did not show evidence of LRO in any of the three Alloy 152 heats aged to an equivalent of 60 years of service. Testing in a primary water environment of two heats of Alloy 152 aged at 370°C to a 60-year service equivalent revealed a fatigue and corrosion fatigue crack growth responses similar to those measured on the un-aged alloys. However, the SCC CGR response of the aged samples appears to show a deterioration in performance, confirming our previous observation.

36 MATERIALS SCIENCE↗
DOE OSTI2026

[C/N] Ages for Red Giants and Their Implications for Galactic Archaeology

Red giants undergo the first dredge-up, a mixing event that creates a connection between their surface [C/N] and their mass and age. We derive a [C/N]–age relationship for red giants calibrated on Apache Point Observatory Galactic Evolution Experiment (APOGEE) DR17 abundances and APOKASC-3 asteroseismic ages. We find that we can use [C/N] to reliably recover asteroseismic ages between 1 and 10 Gyr with average uncertainties of 1.64 Gyr. We find that [C/N] yields concordant ages, with modest offsets, for stars in different evolutionary states. We also find that the [C/N]–birth mass relationship is robust for luminous giants, and argue that this is an advantage over direct asteroseismology for these stars. We use our ages to infer Galactic birth abundance trends in [Fe/H] and [Mg/H] as a function of position in the Galactic disk. We filter out stars with kinematic or chemical properties consistent with migrators and find the number of migrators to be much lower than expected by standard radial migration prescriptions. The remaining population shows weak chemical evolution trends, on the order of 0.01 dex Gyr −1 , over the last 10 Gyr across a wide range of radii.

Roberts, John D. [The Ohio State Univ., Columbus, ↗
DOE OSTI2023

Aging gracefully? Investigating iridium oxide ink's impact on microstructure, catalyst/ionomer interface, and PEMWE performance

Here, in this study, we conducted a thorough investigation of the impact of aging iridium oxide (IrO 2 ) perfluorosulfonic acid ionomer ink for up to 14 days on the properties of the ink and the resulting catalyst layers. We examined ink properties, such as zeta potential, dynamic light scattering (DLS), density, surface tension, and rheology, as functions of ink aging time. To evaluate the microstructure and catalyst/ionomer interface, we employed transmission electron microscopy (TEM), X-ray scattering, and X-ray photoelectron spectroscopy (XPS) techniques. Furthermore, we assessed the effect of ink aging on the performance of proton exchange membrane water electrolyzers (PEMWEs). Our findings reveal that most ink properties remain stable for 14 days. The variations in PEMWE cell performance are minimal, and no clear trend is observed in relation to ink aging time. This study demonstrates that the effects of aging the inks for 14 days on ink properties, catalyst layer structure, catalyst/ionomer interface, and PEMWE performance are negligible, indicating a substantial time window after ink preparation without any significant changes in its properties. These insights provide crucial guidance for the commercial production and coating processes of ink, which is necessary for scaling up PEM technologies to meet future demand.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Impact of specimen preparation method on photovoltaic backsheet degradation during accelerated aging test

In this study, we highlight some important factors in the specimen preparation methods for evaluating photovoltaic backsheet properties after accelerated aging. Two different sequences are considered: Method (I) cut-then-age: cut into 1-cm wide strips and then expose to stress, and Method (II) age-then-cut: expose a larger sheet to stress and then cut into 1-cm widths for mechanical property measurements. We also compare the effect of three cutting methods, (a) tensile specimen punch, (b) paper cutter, and (c) fresh razor blade. Several commercial backsheets were evaluated, with stress exposures including (a) pressure cooker test (PCT), (b) dry ultraviolet (UV) radiation exposure, and (c) UV combined damp heat tests. Fourier transform infrared spectrometer (FTIR) and intrinsic viscosity (IV) were used to analyze the materials on unstressed materials and samples exposed to PCT. The results show that both the cutting method and the time of cutting have an impact on the backsheet mechanical properties. Additionally, under UV exposure, Method II, age-then-cut, generally resulted in a higher average value, with more variation than Method I; however, if the side strips from Method II were excluded, the variation dropped to the same level. This is because the specimens at the sides of the sheet get additional damage from UV light from the exposed sides of the sample. In contrast to UV exposure, PCT specimens prepared by Method II result in lower average values and higher variability. This is attributed to embrittlement through the bulk of the sample where the cutting of embrittled specimens appears to result in more edge defects which can then initiate a break at smaller strains. The data suggest that for UV exposures, the specimens should be cut after aging and the exposed side specimens discarded, and that for PCT exposures, the specimens should be cut before the exposure.

14 SOLAR ENERGY↗
DOE OSTI2025

Long-term thermal aging behavior and strength reduction in a laser powder bed fusion 316H stainless steel

The long-term thermal stability of structural alloys is essential for ensuring the safe and reliable operation of nuclear reactors and other power plants. While extensive research has explored the effects of thermal aging on conventional stainless steels, the behavior of additively manufactured (AM) alloys remains less understood. This study examines the thermal aging response of laser powder bed fusion (LPBF) 316H stainless steel (SS) at temperatures ranging from 550 °C to 750 °C over durations of up to 10,000 h (approximately 1.14 years). Advanced characterization techniques, including electron microscopy and synchrotron X-ray diffraction, were used to investigate dislocation recovery and phase evolution. Based on these findings, a time-temperature-precipitation (TTP) diagram was developed for LPBF 316H SS, revealing a 10- to100-fold acceleration in precipitation kinetics compared to wrought 316H SS. A physics-informed model was calibrated using the short-term experimental data, enabling predictions of average precipitate sizes, volume fractions of M 23 C 6 and Laves phases, and changes in molybdenum solute concentration for aging up to 1 × 10⁶ h (114 years). These microstructural insights were further utilized to estimate yield strength and extrapolate strength reduction factors over the extended aging period. Despite the accelerated aging kinetics, LPBF 316H SS demonstrated superior yield strength retention compared to its wrought counterpart. In conclusion, this study establishes a framework for evaluating long-term performance using short-term experimental data and supports the accelerated qualification of AM materials for high-temperature structural applications.

Laser powder bed fusion↗
DOE OSTI2021

Measurement and Modeling of the effects of exhaust composition and hydrothermal aging on the ammonia storage capacity of a commercial Cu-SSZ-13 catalyst

Copper exchanged chabazites are among the state-of-the-art catalyst materials being studied for selective catalytic reduction of NOx, however, there is still a need to understand how these materials store ammonia after aging. In this work, studies are performed to assess the ammonia storage capacity of Cu-SSZ-13 as a function of concentration, temperature, and extent of hydrothermal aging. Ammonia binds at three difference sites: (i) a Cu site bound at 1 framework Al (Z 1 Cu site), (ii) a Cu site bound at 2 framework Al (Z 2 Cu site), and (iii) a Brønsted acid site (ZH site). Results show that a 3-site model can accurately capture ammonia storage across all conditions. Impacts for hydrothermal aging are considered via 3 aging reactions that change the site densities of each identified adsorption site. Model assessment shows that during aging there is a significant loss in Brønsted acid sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Assessing impact of real-world aging on Cu-redox half cycles of a Cu-SSZ-13 SCR catalyst via transient response measurements and kinetic modeling

We report that the SCR reaction on Cu-SSZ-13 is a redox process consisting of a reduction half-cycle (RHC) and an oxidation half-cycle (OHC). Despite extensive efforts to understand hydrothermal aging and sulfur poisoning, the impact of real-world aging on the SCR activity of Cu-SSZ-13 has not been reported. This work employs a transient response methodology consisting of experiments and kinetic models to investigate the SCR redox cycles at intra-catalyst locations of commercial Cu-SSZ-13 monolith catalysts in their degreened and real-world aged states, in the temperature range of 200–450 °C. Moreover, H 2 -TPR, NH 3 -TPD, SO 2 -TPD, ICP-OES and solid-state NMR were performed to investigate the catalyst properties. Sulfur aging and dealumination caused by real-world exposure decreased the reducible Cu density and SCR performance. Real-world aging was found to selectively slow OHC more than RHC, mainly due to lower mobility of the Cu ions coordinated to sulfur-related species leading to decreased formation of Cu-dimers necessary for OHC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

CH 4 combustion over a commercial Pd/CeO 2 -ZrO 2 three-way catalyst: Impact of thermal aging and sulfur exposure

Thermal aging and sulfur poisoning are major problems influencing the efficiency and lifetime of natural gas three-way catalysts (TWCs) during real-world operation. In the present study, thermal aging and sulfur-induced deactivations on CH 4 combustion were investigated over commercial monolithic honeycombs, i.e., Pd/CexZr 1-x O 2 (CZ)-based TWCs that are thermally aged in the bench (HTA), followed by being operated behind the stoichiometric natural gas engine in high sulfur fuel (HTA + S). In this work, both HTA and HTA + S samples show degraded performance in CH 4 combustion relative to the fresh one, which are caused by the reconstruction of Pd species induced by thermal aging and the decreased reducibility of the support. The 18 O 2 labelling experiments show that in all cases CH 4 combustion proceeds via a MvK mechanism in which lattice O (OL) plays a key role. The sulfation aging (HTA + S sample) promotes the activation of CH 4 and O 2 by forming Pd δ+ -(SO$_4^{2-}$) δ- and Ce 3+ -VO couples at the interface as compared to HTA sample. However, such a promotion effect could be compromised by the blocking effect of sulfate on the exchange of O L from the bulk to the surface and across the surface. The fundamental understanding of thermal and S deactivation mechanisms from this study could help to predict a real-world lifetime use curve of natural gas TWCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗