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Synthesis and study of Pd-Rh alloy nanoparticles and alumina-supported low-content Pd-Rh catalysts for CO oxidation

Highlights: • A bimetallic Pd-Rh/alumina catalyst was prepared using coordination compound. • The peculiarities of precursor decomposition under different media were studied. • Catalytic performance and stability were examined in a CO oxidation reaction. - Abstract: Palladium and rhodium are known to be partly miscible metals. In present work, the peculiarities of coordination compound [Pd(NH{sub 3}){sub 4}]{sub 3}[Rh(NO{sub 2}){sub 6}]{sub 2} decomposition with formation of nanosized solid solutions under different atmospheres were studied by means of thermal gravimetry. Formation of alloy nanoparticles were confirmed by powder X-ray diffraction analysis, scanning and transmission electron microscopies. A bimetallic Pd-Rh/alumina catalyst was prepared by incipient wetness impregnation using coordination compound [Pd(NH{sub 3}){sub 4}]{sub 3}[Rh(NO{sub 2}){sub 6}]{sub 2} as a precursor. Monometallic reference samples were obtained using [Pd(NH{sub 3}){sub 4}](NO{sub 3}){sub 2} and Na{sub 3}[Rh(NO{sub 2}){sub 6}], correspondingly. Catalytic performance and stability of the catalysts were examined in a model reaction of CO oxidation in a prompt thermal aging regime. The environment of precursor decomposition was shown to affect noticeably both the initial activity and stability of the samples in the studied reaction. Reductive atmosphere in comparison with inert and oxidative ones facilitates the formation of the smallest active component species, which demonstrate highest initial activity but worst stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Partial PdAu nanoparticle embedding into TiO 2 support accentuates catalytic contributions from the Au/TiO 2 interface

Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO 2 or TiO 2 supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO 2 and PdAu/TiO 2 , we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO 2 than PdAu/SiO 2 for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO 2 raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO 2 interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO 2 by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO 2 interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO 2 interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO 2 interfacial sites to augment catalytic contributions arising from metal–support interfaces.

Lim, Kang Rui Garrick (ORCID:0000000321599844)↗

Insights into the Dynamic Interfacial and Bulk Composition of Copper-Modified, Hydrogen-Alloyed, Palladium Nanocubes under Electrocatalytic Conditions

Understanding and controlling the alloying properties of nanomaterials under electrochemical conditions are critically important for fields ranging from energy storage and catalysis to electrochromic window technology. Hydrogen-absorbing nanomaterials, like palladium, are especially interesting due to their ability to reversibly absorb and store hydrogen in their lattice at near-stoichiometric amounts. Palladium’s work function is also significantly deeper than that of most transition metals, which enables electrochemical underpotential deposition of conformal monolayer and submonolayer amounts of transition metals onto the palladium surface. The simultaneous existence of these two properties is unique and opens new and exciting avenues for electrochemical applications. However, the intersection of surface-modified, hydrogen-alloyed palladium nanomaterials is poorly understood, and specifically, how these structures evolve during electrochemical operating conditions remains an open question. Here, we synthesize {100}-terminated palladium nanocubes and deposit between 0.5 and 22 monolayers of copper at the palladium surface. We then electrochemically alloy these surface-modified structures with hydrogen. Using a combination of analytical electrochemistry, spectroscopy, and microscopy, we track the positional evolution of the Cu at the surface of Pd, its impact on palladium’s ability to absorb hydrogen, and copper’s effect on hydrogen evolution electrocatalysis. We show that Cu readily alloys into the palladium nanocube at potentials more negative than the Cu 2+/0 deposition, but a 0.5 monolayer thick copper layer remains at the Pd surface regardless of potential. Finally, we discuss the implications of these findings within the framework of CO 2 reduction catalysis for carbon–carbon bond-forming chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excitation temperature of a solution plasma during nanoparticle synthesis

Excitation temperature of a solution plasma was investigated by spectroscopic measurements to control the nanoparticle synthesis. In the experiments, the effects of edge shielding, applied voltage, and electrode material on the plasma were investigated. When the edge of the Ni electrode wire was shielded by a quartz glass tube, the plasma was uniformly generated together with metallic Ni nanoparticles. The emission spectrum of this electrode contained OH, H{sub α}, H{sub β}, Na, O, and Ni lines. Without an edge-shielded electrode, the continuous infrared radiation emitted at the edge created a high temperature on the electrode surface, producing oxidized coarse particles as a result. The excitation temperature was estimated from the Boltzmann plot. When the voltages were varied at the edge-shielded electrode with low average surface temperature by using different electrolyte concentrations, the excitation temperature of current-concentration spots increased with an increase in the voltage. The size of the Ni nanoparticles decreased at high excitation temperatures. Although the formation of nanoparticles via melting and solidification of the electrode surface has been considered in the past, vaporization of the electrode surface could occur at a high excitation temperature to produce small particles. Moreover, we studied the effects of electrodes of Ti, Fe, Ni, Cu, Zn, Zr, Nb, Mo, Pd, Ag, W, Pt, Au, and various alloys of stainless steel and Cu–Ni alloys. With the exception of Ti, the excitation temperatures ranged from 3500 to 5500 K and the particle size depended on both the excitation temperature and electrode-material properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nanoscale Molecules Under Thermodynamic Control:" Digestive Ripening" or " Nanomachining"

Overall Research Goals and Specific Objectives: Nanoscale materials are becoming ubiquitous in science and engineering, and are found widely in nature. However, their formation processes and uniquely high chemical reactivities are not understood well, indeed are often mysterious. Over recent years, a number of research teams have described nanoparticle synthesis, and aging, thermal treatment, or etching times have been mentioned. We have used the terms “digestive ripening” and “nanomachining” and have suggested that thermodynamics plays an important part in the size adjustment to monodisperse arrays being formed. Since there is scant theoretical understanding of digestive ripening, the overall goal in our research is to learn what experimental parameters (ligand used, temperature, solvent, time) are most important, how to control nanoparticle size and shape after initial crude nanoparticles have been synthesized, and gain better understanding of the chemical mechanism details. Specific objectives for the past twentynine months since the grant began have been to (1) Secure and train personnel;as of 2011, a postdoc Deepa Jose, female from the Indian Institute of Science in Bangalore, India; Yijun Sun, a second year graduate student, female from China; and Jessica Changstrom, female from the USA, GK12 fellow (program for enhancing teaching ability) are actively carrying out research. (2) Find out what happens to sulfur bound hydrogen of thiol when it interacts with gold nanoparticles. Our findings are discussed in detail later. (3) Determine the effect of particle size, shape, and temperature on dodecyl thiol assited digestive ripening of gold nanoparticles. See our discussions later. (4) To understand in detail the ligand interaction in molecular clusters and nanoparticles (5) Determine the effect of chain length of amines on Au nanoparticle size under digestive ripening conditions (carbon chain length varied from 4-18). (6) Determine the catalytic activity of gold superlattices obtained by digestive ripening for oxidation of CO to CO2 at room temperature. (7) Determine the photocatalytic activity of metal nanoparticles like Au, Ag,Cu, and Pd supported on TiO2 toward photocatalytic hydrogen production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First principles study on 2H–1T' transition in MoS 2 with copper

In this paper, the electronic properties of MoS 2 are strongly controlled by the structure, providing a route to their modulation. We report, based on first principles calculations, that the adsorption of metal atom Cu on the surface can induce the phase transition of MoS 2 from the semiconducting 2H to the metallic 1T' phase. Cu adsorption results in effective n-type doping of MoS 2 by charge transfer from Cu in the case of the 1T' phase. This is distinct from the behavior in the 2H phase, where Cu does not donate any charge, and it is also distinct from alkali metal adsorption, where charge is donated to both 2H and 1T' MoS 2 . Charge donation to the 1T' phase by Cu stabilizes it with respect to the 2H structure and importantly, it also reduces the energy barrier between the 2H and 1T' structures. This difference reflects the higher electronegativity of Cu, which also indicates that Cu-modified MoS 2 can be expected to be less chemically reactive than MoS 2 with alkali metal adatoms. The main atomic mechanism of the structural transition is the gliding of S atoms on the upper surface. Finally, we report the energetics of the 2H to 1T' transition with several other adatoms, Ag, Au, Ni, Pt and Pd, but none of them are as effective as Cu in inducing the transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

IL-15 induces strong but short-lived tumor-infiltrating CD8 T cell responses through the regulation of Tim-3 in breast cancer

IL-15 has pivotal roles in the control of CD8{sup +} memory T cells and has been investigated as a therapeutic option in cancer therapy. Although IL-15 and IL-2 share many functions together, including the stimulation of CD8 T cell proliferation and IFN-γ production, the different in vivo roles of IL-15 and IL-2 have been increasingly recognized. Here, we explored the different effects of IL-15 and IL-2 on tumor-infiltrating (TI) T cells from resected breast tumors. We found that neither IL-2 nor IL-15 induced intratumoral CD8 T cell proliferation by itself, but after CD3/CD28-stimulation, IL-15 induced significantly higher proliferation than IL-2 during early time points, at day 2, day 3 and day 6. However, the IL-15-induced proliferation leveled off at day 9 and day 12, whereas IL-2 induced lower but progressive proliferation at each time point. Furthermore, IL-15 caused an early and robust increase of IFN-γ in the supernatant of TI cell cultures, which diminished at later time points, while the IL-2-induced IFN-γ production remained constant over time. In addition, the IL-15-costimulated CD8 T cells presented higher frequencies of apoptotic cells. The diminishing IL-15-induced response was possibly due to regulatory and/or exhaustion mechanisms. We did not observe increased IL-10 or PD-1 upregulation, but we have found an increase of Tim-3 upregulation on IL-15-, but not IL-2-stimulated cells. Blocking Tim-3 function using anti-Tim-3 antibodies resulted in increased IL-15-induced proliferation and IFN-γ production for a prolonged period of time, whereas adding Tim-3 ligand galectin 9 led to reduced proliferation and IFN-γ production. Our results suggest that IL-15 in combination of Tim-3 blocking antibodies could potentially act as an IL-2 alternative in tumor CD8 T cell expansion in vitro, a crucial step in adoptive T cell therapy. - Highlights: • We explored the effects of IL-15 and IL-2 on tumor-infiltrating (TI) T cells of breast cancer. • IL-15 and IL-2 had different kinetics in inducing TI CD8 T cell responses. • IL-15 induced stronger but shorter-lived TI CD8 T cell responses than IL-2. • IL-15, but not IL-2, caused upregulation of Tim-3 on TI CD8 T cells. • Blocking Tim-3 resulted in increased IL-15-induced proliferation and IFN-γ production in TI CD8 T cells.

60 APPLIED LIFE SCIENCES↗

CeO 2 Promoted CuO/MgO-Al 2 O 3 Catalyst with Enhanced Activity and Water-Resistance for CO Oxidation

Copper (Cu)-based catalysts have emerged as cost-effective and sustainable alternatives to noble metal systems (e.g., Pt, Pd) for catalytic CO oxidation. However, their practical application is hindered by insufficient low-temperature activity and rapid deactivation under wet conditions containing moisture. To address these challenges, this work introduces CeO 2 -modified CuO/MgO-Al 2 O 3 (Cu-Ce/MA) catalysts, strategically designed to enhance the catalytic performance and water resistance simultaneously. These catalytic materials were evaluated for CO oxidation under both dry and humid conditions, revealing that CeO 2 modification significantly improves the low-temperature activity. Specifically, the optimal catalyst, Cu-30Ce/MA, achieved a 50% CO conversion temperature (T 50 ) of 151 °C, a marked reduction from 218 °C on Cu/MA reference catalyst. Furthermore, the water resistance improves in a CeO 2 content-dependent manner, with higher CeO 2 loadings imparting greater stability in humid environments. Detailed characterizations demonstrate that CeO 2 promotes the dispersion of CuO and stabilizes Cu sites, while also enhancing the low-temperature reducibility and CO adsorption capacity. Crucially, CeO 2 modification suppresses the competitive H 2 O adsorption, mitigating water-induced deactivation. These synergistic effects collectively rationalize the superior activity and durability of Cu-Ce/MA catalysts. By elucidating the dual role of CeO 2 in optimizing Cu-based systems, this study advances the rational design of cost-effective catalysts for real-world CO emission control, particularly under water-rich industrial conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Increasing Al-Pair Abundance in SSZ-13 Zeolite via Zeolite Synthesis in the Presence of Alkaline Earth Metal Hydroxide Produces Hydrothermally Stable Co-, Cu- and Pd-SSZ-13 Materials

Replacing alkaline for alkaline-earth metal hydroxide in the synthesis gel during the synthesis of siliceous SSZ-13 zeolite (Si/Al~10) yields SSZ-13 with novel, advantageous properties. Its NH 4 -form ion-exchanges higher amount of isolated divalent M(II) ions than the conventional one: this is the consequence of an increased number of Al pairs in the structure induced by the +2 charge of Sr(II) cations in the synthesis gel that force two charge-compensating AlO 4 – motives to reside closer together. We characterize the +2 state of Co(II) ions in these materials with infra-red spectroscopy and X-ray absorption spectroscopy measurements and show their utility for NOx pollutant adsorption from ambient air: the ones derived from SSZ-13 with higher Al pair content contain more isolated cobalt(II) and, thus, perform better as ambient-air NOx adsorbers. Notably, Co(II)/SSZ-13 with an increased number of Al pairs is significantly more hydrothermally stable than its NaOH-derived analogue. Loading Pd(II) into Co-SSZ-13(Sr) produces an active NOx adsorber (PNA) material that can be used for NOx adsorption from simulated diesel engine exhaust. The critical issue for these applications is hydrothermal stability of Pd-zeolites. Pd/SSZ-13 synthesized in the presence of Sr(OH) 2 does not lose its PNA capacity after extremely harsh aging at 850 and 900 °C (10 h in 10% H 2 O/air flow) and loses only ~55% capacity after hydrothermal aging at 930 °C. This can be extended to other divalent metals for catalytic applications, such as copper: we show that Cu/SSZ-13 catalyst can survive hydrothermal aging at 920 °C without losing its catalytic properties, metal dispersion and crystalline structure. Thus, we provide a new, simple, and scalable strategy for making remarkably (hydro)thermally stable metal-zeolite materials/catalysts with a number of useful applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intra-catalyst CH 4 oxidation pathways on a Pd/Al 2 O 3 /CeZrO x -based commercial catalyst and implications on NO x conversion profiles for a natural gas vehicle exhaust under lambda modulation

The performance of a three-way catalyst (TWC) in natural gas-powered vehicles is enhanced by periodic changes in air-to-fuel ratio (λ-modulation). The reaction networks and sequences inside the catalyst that facilitate such enhanced performance have not been extensively investigated. Here, this work applied intra-catalyst measurements (SpaciMS) to analyze the transient spatiotemporal gas concentrations inside a Pd-based TWC to establish relationships between CH 4 , NO x , CO and H 2 conversion pathways. Steam reforming and partial oxidation were revealed to be the main CH 4 conversion routes. The cyclic rich-lean conditions combined with the oxygen storage capacity (OSC) of the TWC generate reduced and oxidized zones that are constantly moving within the catalyst, changing the dominant chemical reactions occurring on the surface. In the reduced zones, OSC is depleted while CH 4 is converted through steam reforming and NO x is converted through reactions with H 2 , CO, and other surface-bound reducing fragments formed by CH 4 conversion. In the oxidized zones, OSC is replenished, CH 4 is converted by partial oxidation, and H 2 , CO, and NH 3 are oxidized. The length of lean-rich phases impacts the catalyst performance significantly; too short or too long of a rich or lean phase can lower the overall conversion of reactive species. An inhibition of CH 4 conversion was observed during the rich phase possibly due to CO-poisoning of active sites. The intra-catalyst measurements revealed that the catalyst consists of three distinct reaction zones and their lengths vary with modulation conditions. Various modulation frequencies, amplitudes, λ-centers, and temperatures were investigated which allowed an understanding of how these parameters affect the reaction zones and catalyst utilization. Understandings from this work can enable adaptive λ-control strategies to optimize the overall TWC performance over a range of vehicle operating conditions.

Lean-Rich cycling↗

Atomistic mechanisms for catalytic transformations of NO to NH3, N2O, and N2 by Pd

The industrial pollutant NO is a potential threat to the environment and to human health. Thus, selective catalytic reduction of NO into harmless N2, NH3, and/or N2O gas is of great interest. Among many catalysts, metal Pd has been demonstrated to be most efficient for selectivity of reducing NO to N2. However, the reduction mechanism of NO on Pd, especially the route of N−N bond formation, remains unclear, impeding the development of new, improved catalysts. We report here the elementary reaction steps in the reaction pathway of reducing NO to NH3, N2O, and N2, based on density functional theory (DFT)-based quantum mechanics calculations. We show that the formation of N2O proceeds through an Eley-Rideal (E−R) reaction pathway that couples one adsorbed NO* with one non−adsorbed NO from the solvent or gas phase. This reaction requires high NO* surface coverage, leading first to the formation of the trans-(NO)2* intermediate with a low N−N coupling barrier (0.58 eV). Notably, trans-(NO)2* will continue to react with NO in the solvent to form N2O, that has not been reported. With the consumption of NO and the formation of N2O* in the solvent, the Langmuir-Hinshelwood (L-H) mechanism will dominate at this time, and N2O* will be reduced by hydrogenation at a low chemical barrier (0.42 eV) to form N2. In contrast, NH3 is completely formed by the L-H reaction, which has a higher chemical barrier (0.87 eV). Our predicted E-R reaction has not previously been reported, but it explains some existing experimental observations. In addition, we examine how catalyst activity might be improved by doping a single metal atom (M) at the NO* adsorption site to form M/Pd and show its influence on the barrier for forming the N−N bond to provide control over the product distribution.

Physics↗

Structural insights into the oligomerization of FtsH periplasmic domain from Thermotoga maritima

Highlights: • We report the 1.5–1.95A resolution crystal structures of the Thermotoga maritima FtsH periplasmic domain (tmPD). • Acidic residues at the pore region of tmPD are highly conserved among only the thermophilic, FtsH homologs. • The negative charge repulsion of tmPD destabilizes its hexamerization. • Dynamical features of the PD in hexameric full-length FtsH may be relevant for the substrate recognition. Prompt removal of misfolded membrane proteins and misassembled membrane protein complexes is essential for membrane homeostasis. However, the elimination of these toxic proteins from the hydrophobic membrane environment has high energetic barriers. The transmembrane protein, FtsH, is the only known ATP-dependent protease responsible for this task. The mechanisms by which FtsH recognizes, unfolds, translocates, and proteolyzes its substrates remain unclear. The structure and function of the ATPase and protease domains of FtsH have been previously characterized while the role of the FtsH periplasmic domain has not clearly identified. Here, we report the 1.5–1.95 Å resolution crystal structures of the Thermotoga maritima FtsH periplasmic domain (tmPD) and describe the dynamic features of tmPD oligomerization.

60 APPLIED LIFE SCIENCES↗

Fundamental Studies of Bifunctional Catalysts for Tandem Reactions

During the past few years of our funding from DOE Basic Energy Sciences, we have focused on the catalytic conversion of biomass-derived 5-hydroxymethyl furfural (HMF) as a platform molecule for sustainable synthesis of value-added chemicals. The combination of the diene and aldehyde functionalities in HMF enables catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Whereas the electron-withdrawing nature of aldehyde group inhibits the reactivity of diene group in HMF to undergo Diels-Alder reactions with dienophiles, by converting the aldehyde group in HMF to an electron-donating hydroxyl group, HMF can append maleimide-based chemicals through Diels-Alder coupling. Acetalization of HMF not only produces an electron-rich diene for Diels-Alder reaction, but it also alters the reversibility of acetal formation and thereby allows for the controlled release of chemicals by hydrolysis. Therefore, we synthesized various norcantharimide derivatives from biomass-derived HMF by acetalization over an acid catalyst, Amberlyst-15, followed by Diels-Alder reaction with maleimide. The norcantharimides release the starting materials by retro Diels-Alder reaction that is triggered by acetal hydrolysis under acidic (≤pH 3) conditions. In subsequent work, we explored the synthesis and properties of functional polyurethanes and polyesters with tunable properties from biomass-derived (HMF)-Acetone-HMF (HAH) monomers. HAH can be selectively hydrogenated over Cu and Ru catalysts to produce partially-hydrogenated HAH (PHAH) and fully-hydrogenated HAH (FHAH). HAH contains functional groups, including hydroxyl, furan, enone, and ketone functionalities, that can be exploited to further tune the polymer properties. The π-electron conjugation between the enone and furan groups in HAH monomer stabilizes the furan group to prevent the uncontrolled degradation of furans during reactions, such as etherification. Therefore, HAH is a renewable monomer that can be used to synthesize polymers, having high molecular weight, symmetric functionalities, an inexpensive production price, and being derived from renewable resources without competition with food resources. We demonstrated the synthesis of functional polyurethanes and a renewable polyester from HAH-derived monomers, and 4,4’-methylenebis(phenyl isocyanate) (MDI). We showed that it is essential to be able to selective hydrogenate C=C double bonds in HAH to be able to achieve effective Diels Alder reactions of the furan ring. Therefore, we studied the hydrogenation at temperatures from 313 – 393 K of HAH over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. A 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, a 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Using the results from our detailed reaction kinetics studies, we developed universal conditions for the maximum production of the various hydrogenated products for both batch and plug flow systems. In subsequent work, we employed reaction schemes to optimize the yields of products from selective hydrogenations of HAH in isopropanol solvent and in the presence of liquid water. Reaction schemes consisting of 7, 9, and 11 steps were examined to describe the rates of formation of the observed products and reaction intermediates for hydrogenation of HAH over Ru and Pd catalysts, and a 3-step scheme was studied over Cu catalysts. Rate constants and activation energies were calculated using these reaction schemes, and we then apply these reaction schemes to explore the effects of water addition on the hydrogenation pathways. The effects of water addition to isopropanol (IPA) solvents on the hydrogenation of HAH were markedly different over Pd, Ru, and Cu catalysts. Over the Pd catalyst, the addition of water to IPA increased hydrogenation rates and promoted hydrogenation of furan rings. The addition of water to IPA yielded significant carbon losses over the Ru catalyst, and slowed hydrogenation steps over Cu, while significantly inhibiting hydrogenation of the ketone group. This behavior opened routes toward increased production rates of PHAH=O (a partially hydrogenated form of HAH containing a C=O bond), a product in which the diene groups of the furan rings were not hydrogenated. Addition of water also allowed increased feed concentrations of HAH that were previously not possible in pure IPA solvents.

09 BIOMASS FUELS↗

Alzheimer's disease and alpha-synuclein pathology in the olfactory bulbs of infants, children, teens and adults ≤ 40 years in Metropolitan Mexico City. APOE4 carriers at higher risk of suicide accelerate their olfactory bulb pathology

Highlights: • Air pollution targets olfactory bulbs in young city dwellers. • Olfactory bulb hyperphosphorylated tau and Lewy neurites are present in Mexico City toddlers. • APOE4 carriers accelerate their OB pathology and have 4.7 times higher suicide odds v APOE3. • Olfactory testing may aid in identifying young persons at high risk for neurodegenerative disease. • Early neuroprotective interventions in PM{sub 2.5} and CDNP's exposed individuals ≤ 20 years are critical. There is growing evidence that air pollution is a risk factor for a number of neurodegenerative diseases, most notably Alzheimer's (AD) and Parkinson's (PD). It is generally assumed that the pathology of these diseases arises only later in life and commonly begins within olfactory eloquent pathways prior to the onset of the classical clinical symptoms. The present study demonstrates that chronic exposure to high levels of air pollution results in AD- and PD-related pathology within the olfactory bulbs of children and relatively young adults ages 11 months to 40 years. The olfactory bulbs (OBs) of 179 residents of highly polluted Metropolitan Mexico City (MMC) were evaluated for AD- and alpha-synuclein-related pathology. Even in toddlers, hyperphosphorylated tau (hTau) and Lewy neurites (LN) were identified in the OBs. By the second decade, 84% of the bulbs exhibited hTau (48/57), 68% LNs and vascular amyloid (39/57) and 36% (21/57) diffuse amyloid plaques. OB active endothelial phagocytosis of red blood cell fragments containing combustion-derived nanoparticles (CDNPs) and the neurovascular unit damage were associated with myelinated and unmyelinated axonal damage. OB hTau neurites were associated mostly with pretangle stages 1a and 1b in subjects ≤ 20 years of age, strongly suggesting olfactory deficits could potentially be an early guide of AD pretangle subcortical and cortical hTau. APOE4 versus APOE3 carriers were 6–13 times more likely to exhibit OB vascular amyloid, neuronal amyloid accumulation, alpha-synuclein aggregates, hTau neurofibrillary tangles, and neurites. Remarkably, APOE4 carriers were 4.57 times more likely than non-carriers to die by suicide. The present findings, along with previous data that over a third of clinically healthy MMC teens and young adults exhibit low scores on an odor identification test, support the concept that olfactory testing may aid in identifying young people at high risk for neurodegenerative diseases. Moreover, results strongly support early neuroprotective interventions in fine particulate matter (PM{sub 2.5}) and CDNP's exposed individuals ≤ 20 years of age, and the critical need for air pollution control.

54 ENVIRONMENTAL SCIENCES↗

Analysis of Launch Vehicle Liftoff Debris: Historical Perspective from Space Shuttle and Application to Artemis I

Human exploration-class launch vehicles are inherently prone to debris due to the extreme environments generated during pre-launch operations, liftoff, and flight. The use of cryogenic propellants often requires thermal protection system (TPS) coatings, typically foam, to maintain the propellant conditions in the tank and prevent an accumulation ice on the external surface of the vehicle. Some ice growth is to be expected at umbilical interfaces, vents, flanges, or brackets where it is difficult to apply TPS. This ice may come loose at any time due to wind on the launch pad, structural vibration and acoustics after rocket ignition, or aerodynamic forces during flight. This phenomena is especially apparent on vehicles with no TPS, such as the Saturn V rockets used in the Apollo Program, see Figure 1. During propellant tanking, the thermal contraction of the underlying substrate may generate cracks in the TPS (Figure 1). Chunks of TPS can release due to the expansion of ingested gas from cryopumping or from aerodynamic forces if the crack creates an offset surface. Most foams will also have a certain amount of “popcorning” where small pieces of foam will pop off during flight because of the differential between the static surface pressure and the pressure of the gas trapped in the foam cell structure. There are a number of other coating or closeout materials that may be shed from the vehicle and become debris. During pre-launch operations and liftoff, the vehicle may also be exposed to debris originating from the launch pad or ground support equipment. This debris is separate from foreign object debris, or FOD, which is not intended to be present and is strictly controlled through operations and maintenance procedures. In this case, debris is generated from hardware and materials that are necessary for launch and are subject to the intense vibration, acoustics, and direct plume impingement of the launch environment. Examples include ice from umbilicals, tape and tie wraps that protect cables, and rust or corrosion from the launch platform. While NASA has historically been aware of debris as a potential issue that could cause a failure resulting in loss of mission, loss of vehicle, or loss of crew, the likelihood and severity of that risk was not always well understood or given sufficient weight in program and flight decisions. After the Space Shuttle Columbia accident (STS-107), the investigation found that foam TPS debris shed from the external tank was the proximate cause of the damage to the orbiter wing. Six previous observations of debris released from the foam ramp that covered the bipod connecting the forward end of the orbiter to the external tank resulted in minor changes or were determined to be accepted flight risks. Two occurrences of bipod ramp foam loss were not identified until the STS-107 investigation. Despite the damage inflicted by these debris strikes, the Shuttle Program Requirements Control Board deemed the vehicle safe to fly. During the Return to Flight effort following the Columbia disaster, NASA Engineering developed a process for the assessment of debris transport, impact, and damage tolerance to support independent assessments of risk by NASA Safety and Mission Assurance (S&MA). Under this system, each element (vehicle or ground system) defines a catalog of all expected debris based on launch history, component testing, or analysis. Debris transport analysis (DTA) is conducted using the debris catalog characteristics and potential flow transport mechanisms (e.g., vehicle aerodynamics, gravity, wind, plume-driven). The predicted debris impact locations and velocities are provided to the hardware owners, who use available test data and analysis to determine whether each component can withstand the impacts. In cases where the element hardware may be severely damaged or fail, the options are to mitigate the debris source through some change in design or operation, or to work with S&MA to try to characterize the probability of the impact and damage for program risk acceptance. Because of the differences in debris characteristics and transport, the DTA has been divided between the Liftoff and Ascent regimes. The development and application of Liftoff DTA methodology from the Shuttle Program to the current Artemis Program is the subject of this paper. Liftoff DTA covers the time from the start of pre-launch operations at the launch pad, up until the vehicle clears the launch tower and there is no longer any interaction with ground systems. Debris transport during this period is broadly classified as either gravity, wind, and plume-entrained (GWPE) or plume driven (PD). GWPE debris is generally lower speed, travelling in a forward-to-aft direction. PD transport includes flow features from the rocket ignition transient, as well as plume impingement and recirculation that occur as the vehicle lifts off the launch platform. In these cases, the debris typically moves in an aft-to-forward direction at higher speeds. The applicable transport mechanisms must be considered for each piece of debris depending on the material, and release location and time. For example, rust or metallic debris from the tower could fall (GWPE) and impact the vehicle before landing on the launch platform deck where it could be also be transported by plume impingement (PD). However, falling ice (GWPE) from an umbilical is unlikely to survive impact with the vehicle or launch platform and be available for PD transport. Modeling of debris transport is accomplished using a set of DTA tools which simulate debris trajectories subject to a reference frame acceleration (i.e., gravity) and aerodynamic drag. Where the trajectory encounters a solid surface, the debris is allowed to rebound with a specified coefficient of restitution. The drag is calculated by interpolating the fluid state at each point in the debris trajectory from high-fidelity computational fluid dynamics (CFD) simulations of the launch vehicle and pad. The CFD data may either be static (steady state or time averaged), typically for GWPE transport, or dynamic (time-accurate) for PD flow features like the ignition transient. Examples of the CFD flow field solutions for the Space Launch System (SLS) rocket and launch pad are shown in Figure 2. Typical SLS debris trajectory predictions from DTA are illustrated in Figure 3. The final version of this paper will include a more detailed examination of the Liftoff DTA process developed during the Shuttle Program, and how it has been augmented and applied to the SLS rocket under the Artemis Program. Comparisons with debris observations from the Artemis I launch will demonstrate validation of the tools and methodology.

Debris↗

SPHERES: From Ground Development to Operations on ISS

SPHERES (Synchronized Position Hold Engage and Reorient Experimental Satellites) is an internal International Space Station (ISS) Facility that supports multiple investigations for the development of multi-spacecraft and robotic control algorithms. The SPHERES Facility on ISS is managed and operated by the SPHERES National Lab Facility at NASA Ames Research Center (ARC) at Moffett Field California. The SPHERES Facility on ISS consists of three self-contained eight-inch diameter free-floating satellites which perform the various flight algorithms and serve as a platform to support the integration of experimental hardware. To help make science a reality on the ISS, the SPHERES ARC team supports a Guest Scientist Program (GSP). This program allows anyone with new science the possibility to interface with the SPHERES team and hardware. In addition to highlighting the available SPHERES hardware on ISS and on the ground, this presentation will also highlight ground support, facilities, and resources available to guest researchers. Investigations on the ISS evolve through four main phases: Strategic, Tactical, Operations, and Post Operations. The Strategic Phase encompasses early planning beginning with initial contact by the Principle Investigator (PI) and the SPHERES program who may work with the PI to assess what assistance the PI may need. Once the basic parameters are understood, the investigation moves to the Tactical Phase which involves more detailed planning, development, and testing. Depending on the nature of the investigation, the tactical phase may be split into the Lab Tactical Phase or the ISS Tactical Phase due to the difference in requirements for the two destinations. The Operations Phase is when the actual science is performed; this can be either in the lab, or on the ISS. The Post Operations Phase encompasses data analysis and distribution, and generation of summary status and reports. The SPHERES Operations and Engineering teams at ARC is composed of experts who can guide the Payload Developer (PD) and Principle Investigator (PI) in reaching critical milestones to make their science a reality using the SPHERES platform. From performing integrated safety and verification assessments, to assisting in developing crew procedures and operations products, to organizing, planning, and executing all test sessions, to helping manage data products, the SPHERES team at ARC is available to support microgravity research with the SPEHRES Guest Scientist Program.

ISS Research↗

Realistic multisite lattice-gas modeling and KMC simulation of catalytic surface reactions: Kinetics and multiscale spatial behavior for CO-oxidation on metal (100) surfaces

A realistic molecular-level description of catalytic reactions on single-crystal metal surfaces can be provided by stochastic multisite lattice-gas (msLG) models. This approach has general applicability, although in this report, we will focus on the example of CO-oxidation on the unreconstructed fcc metal (100) or M(100) surfaces of common catalyst metals M = Pd, Rh, Pt and Ir (i.e., avoiding regimes where Pt and Ir reconstruct). These models can capture the thermodynamics and kinetics of adsorbed layers for the individual reactants species, such as CO/M(100) and O/M(100), as well as the interaction and reaction between different reactant species in mixed adlayers, such as (CO + O)/M(100). The msLG models allow population of any of hollow, bridge, and top sites. This enables a more flexible and realistic description of adsorption and adlayer ordering, as well as of reaction configurations and configuration-dependent barriers. Adspecies adsorption and interaction energies, as well as barriers for various processes, constitute key model input. The choice of these energies is guided by experimental observations, as well as by extensive Density Functional Theory analysis. Model behavior is assessed via Kinetic Monte Carlo (KMC) simulation. We also address the simulation challenges and theoretical ramifications associated with very rapid diffusion and local equilibration of reactant adspecies such as CO. These msLG models are applied to describe adsorption, ordering, and temperature programmed desorption (TPD) for individual CO/M(100) and O/M(100) reactant adlayers. In addition, they are also applied to predict mixed (CO + O)/M(100) adlayer structure on the nanoscale, the complete bifurcation diagram for reactive steady-states under continuous flow conditions, temperature programmed reaction (TPR) spectra, and titration reactions for the CO-oxidation reaction. Extensive and reasonably successful comparison of model predictions is made with experimental data. Furthermore, we discuss the possible transition from traditional mean-field-type bistability and reaction kinetics for lower-pressure to multistability and enhanced fluctuation effects for moderate- or higher-pressure. Behavior in the latter regime reflects a stronger influence of adspecies interactions and also lower diffusivity in the higher-coverage mixed adlayer. We also analyze mesoscale spatiotemporal behavior including the propagation of reaction diffusion fronts between bistable reactive and inactive states, and associated nucleation-mediated transitions between these states. This behavior is controlled by complex surface mass transport processes, specifically chemical diffusion in mixed reactant adlayers for which we provide a precise theoretical formulation. The msLG models together with an appropriate treatment of chemical diffusivity enable equation-free heterogeneous coupled lattice-gas (HCLG) simulations of spatiotemporal behavior. In addition, msLG + HCLG modeling can describe coverage variations across polycrystalline catalysts surfaces, pressure variations across catalyst surfaces in microreactors, and could be incorporated into a multiphysics framework to describe mass and heat transfer limitations for high-pressure catalysis. (C) 2013 Elsevier Ltd. All rights reserved.

36 MATERIALS SCIENCE↗

Precious Metal Distributions in Direct Nickel Matte Smelting with Low-Cu Mattes

Base metal (Cu, Fe, and Ni) and trace element (Ag, Au, Co, Pd, and Pt) distributions between low-iron nickel mattes with [Ni]:[Cu] = 4 (w/w) have been studied at 1623 K to 1723 K (1350 °C to 1450 °C). We equilibrated small slag–matte samples with CO–CO{sub 2}–SO{sub 2}–Ar atmospheres in pre-selected P{sub S{sub 2}}–P{sub O{sub 2}} points, maintaining silica saturation by fused silica crucibles. The slags studied contained about 0 to 8.5 wt pct MgO. The matte–slag distribution coefficients L{sup m/s}[Me] were obtained from assays by electron probe X-ray microanalysis for the matte and by laser ablation-ICP-mass spectrometry for the slag. The measured L{sup m/s}[Me] values were clearly dependent on iron concentration of the matte and on MgO concentration of the slag, with values on the order of 10{sup 4}, 10{sup 5}, and 10{sup 4} for gold, platinum, and palladium, respectively, in the 5 wt pct iron in matte experiments. The obtained data for silver were scattered, due to volatilization, resulting in depletion of most silver and its escape from matte to gas phase during the 3-hour equilibration period. The matte-to-slag distribution coefficient for silver was estimated to be L{sup m/s}[Ag] = 100 to 400. We also measured the distributions of the base metals Cu and Ni in the same conditions as the trace elements.

36 MATERIALS SCIENCE↗