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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A chiral alkali metal capped Ni 4 cubane complex: Synthesis, structure, magnetic and catalytic bromination studies

A new chiral NaO 2 Ni 4 O 2 N 2 cluster has been developed with a distorted capped cubane-type structure. The structure was determined by single crystal X-ray diffraction. The tetradentate Schiff-base ligand was synthesized by the condensation of o-vanillin and $\textit{D}$-(-)–threo-2-amino-1-(4-nitrophenyl)-1,3-propanediol. X-ray structure reveals that the complex possesses a Ni 4 cubane cluster where sodium ion is anchored on the face of the cubane structure. Continuous shape measurement studies revealed that all the Ni centres are in distorted octahedral geometry and sodium ion adopts the spherical square pyramidal geometry. Further structural exploration reveals that the complex shows local distortions of the coordination geometries at each metal site, and these distortions govern the magnetic anisotropy associated with each Ni II ion. For the present case, an elongation ($d_{str}$ > 0) of the octahedral coordination sphere results in a local easy-plane anisotropy, with a positive $D_{Ni(II)}$ parameter. Temperature dependant magnetization measurements showed a predominant ferromagnetic interaction amongst the four Ni centres. This complex is also catalytically active towards bromination of aromatic phenolic compounds. Initial catalytic activity was verified with the conversion of phenol red to bromophenol blue. Different phenolic substances show good conversion to their corresponding bromo derivatives. The complex showed good catalytic activity towards bromination of aromatic phenolic compounds, offering up to 99% conversion with 100% selectively to their corresponding bromo derivatives.

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

Effect of Solvent on the Interaction of Lignin with a Zeolite Nanosheet in the Condensed Phase

Lignin is the essential building block of lignocellulosic biomass, an excellent renewable source of different aromatic monomers for the polymer and biofuel industry. The depolymerization of lignin into value-added chemicals and fuels through the catalytic process poses a significant challenge due to the complex structure of lignin. Understanding lignin’s conformational diversity and dynamics in the liquid phase is crucial to designing an effective depolymerization process. Here, we conducted all-atom molecular dynamics simulations to understand the conformation and dynamics of softwood lignin on the all-silica zeolite nanosheet based on the MFI topology in a binary mixture of water–methanol at three different molar compositions (0%, 50%, and 100% methanol). We observed that the methanol–surface interaction is stronger than the water–surface interaction, and methanol readily diffused into the MFI core. Lignin surface contacts decrease with increasing methanol composition due to higher solubility and dynamics. Lignin dynamics on the surface in neat water is an order of magnitude smaller than methanol. Here, we also found that lignin adopts a slightly extended conformation when it stays on the surface than in the bulk solution phase for the pure water case, whereas for pure methanol and the binary solution structures are statistically similar.

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

Review of Experimental Decontamination Factors (DF) of Iodine in the Pilot-Scale Law Melter Off-Gas Systems

The Low Activity Waste (LAW) melters at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will convert low-activity tank wastes containing high concentrations of sodium salts into glass for onsite disposal. Much of the airborne particulates during the calcination/fusion of the feed solids will be removed by condensation and scrubbing of the melter exhaust in the Submerged Bed Scrubber (SBS) and Wet Electrostatic Precipitator (WESP)of the primary off-gas treatment system. The gases exiting the WESP enter a secondary off-gas treatment system, which includes a High-Efficiency Particulate Air (HEPA) filter, an activated carbon absorber, a Thermal Catalytic Oxidizer (TCO), a Selective Catalytic Reduction (SCR) unit, a caustic scrubber, and an exhauster. Much of the volatile organics and NOx will be removed in the TCO and SCR, respectively. Under WTP Direct Feed LAW (DFLAW) configuration, the liquid effluents from the SBS and WESP will be collected and evaporated under vacuum with the evaporator concentrate recycled back to the LAW melter, while the evaporator condensate will be merged with the caustic scrubber solution and sent to the Effluent Treatment Facility (ETF).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Demonstrating the Critical Role of Solvation in Supported Ti and Nb Epoxidation Catalysts via Vapor-Phase Kinetics

Catalytic oxidation of hydrocarbons with hydrogen peroxide (H 2 O 2 ) has been of the utmost importance for several decades. The vast majority of studies have been performed in the condensed phase, even though condensed phases introduce complex solvent effects and can promote the leaching of active sites. In response, we have built a custom reactor system to understand H 2 O 2 activation and selective oxidation in the vapor-phase. In this report, we study the epoxidation of cyclohexene with H 2 O 2 over four Lewis-acidic metal oxide catalysts: Ti and Nb grafted on SiO 2 and on the Zr based metal–organic framework, NU-1000. The M–SiO2 materials are highly selective to the formation of epoxides and diols, as they can be in the condensed phase, while the NU-1000 based materials are far more prone to overoxidation to CO 2 , which appears to be connected to their strong reactant adsorption. Apparent activation energies are calculated for all materials when operating in the same kinetic regime, and the heats of cyclohexene adsorption into their pores are then used to directly compare intrinsic enthalpies of activation in the vapor vs condensed phase for the M–SiO 2 catalysts. Nb–SiO 2 catalysts exhibit similar intrinsic enthalpies of activation in the vapor and condensed phases, whereas the condensed phase transition state in Ti–SiO 2 is 24 kJ/mol lower in energy than that of the same material in the vapor phase. These experiments establish another methodology for understanding the various roles of solvent in selective oxidation reactions and studying these reactions under conditions that differ significantly from the thousands of prior studies in the condensed phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1995

Formation of Hydrocarbons in the Outflows from Red Giants

The formation of hydrocarbons in the oxygen-rich outflows from red giants was studied. The existence of organic molecules in such outflows has been known for several years; however, their surprisingly high abundances has been a mystery since all of the carbon had been thought to be irretrievably locked up in CO, the most strongly bound molecule. CO is the first molecule to form from the atoms present in the star's extended atmosphere, and as strong stellar winds drive a cooling outflow, dust grains condense out. In oxygen-rich outflows, the dust is thought to be composed mainly of silicates and other metal oxides. Perhaps the noble metals can condense out in metallic form, in particular the relatively abundant transition metals iron and nickel. We proposed that perhaps the carbon reservoir held as CO can be accessed through a catalytic process involving the chemisorption of CO and H2 onto grains rich in metallic iron. CO and H2 are the two most abundant molecules in circumstellar outflows, and they both are known to dissociate on transition metal surfaces at elevated temperatures, freeing carbon to form organic molecules such as methane. We believe methane is a precursor molecule to the organics observed in oxygen-rich red giants. We have developed a nonequilibrium numerical model of a surface chemical (catalytic) process. Based on this model, we believe that methane can be formed under the conditions present in circumstellar outflows. Although the methane formation rates are exceptionally low under these conditions, over dynamical timescales, a significant amount of CO can be converted to methane and driven further out in the envelope, explaining the presence of organics there.

Roberge, Wayne↗
DOE OSTI2023

Catalytic Upgrading of Carbohydrates in Waste Streams to Hydrocarbons: Paper Sludge to Fuel Project (PStF)

This research, funded by the Department of Energy Bioenergy Technologies Office (DOE BETO), aims to understand the barriers and assess opportunities for transforming carbohydrates in paper sludge, a solid lignocellulosic residue from the pulp and paper industry. The goal is to turn the paper sludge into a liquid hydrocarbon product that can be blended into jet fuel, both economically and sustainably. Research groups at North Carolina State University, National Renewable Energy Laboratory, and Yale University collaborated synergistically, leveraging their expertise in pulp and paper operations, biomass deconstruction, and catalytic upgrading to propose a pathway that efficiently captures the energy in paper sludge. Findings from this study could potentially contribute to advancing biomass conversion technologies, aligning with the efforts of the U.S. DOE BETO. This report documents the experimental and simulation results of a biochemical and catalytic pathway designed to transform paper sludge into a liquid hydrocarbon product. The process involves a sequence of seven steps, including ash removal, carbohydrate enzymatic hydrolysis, sugar dehydration, solvent recovery, aldol-condensation between furans and ketone, hydrogenation, and hydrodeoxygenation to obtain a hydrocarbon blend in the ~C10 range. The experimental efforts from the initiation of the project were guided by techno-economic analysis (TEA) and sensitivity analysis results including around seventy-eight operational parameters. This methodology facilitated the efficient use of resources over time. This study relies on detailed process simulations and TEA to determine the minimum fuel selling price (MFSP) for the hydrocarbon fuel product. Preliminary TEA results led to the evaluation of eight case studies considering alternative dehydration co-solvents, operational settings, and biorefinery layouts. Finally, the life cycle assessment of twenty-eight scenarios, comparing various dehydration co-solvents, fuel sources, chemical feedstock sources, side product utilization, and other process settings, was conducted. Landfilling scenarios with and without landfill gas recovery were also estimated, analyzed, and compared.

09 BIOMASS FUELS↗
NASA NTRS1975

Edible carbohydrates from formaldehyde in a spacecraft

The autocatalytic nature of the base catalyzed condensation of formaldehyde to formose sugars is eliminated by using as a cocatalyst, an aldose, or ketose having an alpha-hydrogen. This is more strongly complexed by base than is formaldehyde and the cocatalyst and sugar products accumulate as catalyst complexes instead of formaldehyde. Because of the presence of alpha-hydrogen atoms in cocatalysts and formose sugars, their removal by cross Cannizzaro reaction of complexed sugars does not occur, so the formose reaction behaves autocatalytically due to this accumulation. It is believed that a given catalytic formose complex is not a discrete complexed sugar, but rather, a scrambled dynamic mixture of sugars having weakened structures. The sugar complexes derive from a common salt-like formaldehyde complex, which, because of the absence of alpha-hydrogen, has a greater tendency to undergo Cannizzaro reaction, rather than formose condensation. Because of this, the Cannizzaro reaction can proceed without measurable formose condensation. The reverse is not possible.

Weiss, A. H.↗
DOE OSTI2024

Synthesis of aviation biofuel precursors from biomass-derived ketones: Substrate adsorption configuration-catalytic activity

The production of aviation biofuel precursors from biomass-derived ketones by heterogeneous catalysis has been hindered by the low catalytic activity. Herein, a series of Cu-doped metal oxide catalysts were prepared for the conversion of biomass-derived ketones to aviation biofuel precursors. Solvent-free cyclopentanone conversion via aldol condensation reached 91.1 % over Cu/Al 2 O 3 with 100 % selectivity toward dimer and trimer oxygenated species, all of which are aviation biofuel precursors. This catalyst primarily contains Cu 2 O and Cu nanoparticles which are uniformly dispersed across the Al 2 O 3 surface. From in situ DRIFTS and DFT results, the incorporation of Cu species onto Al 2 O 3 not only increased the diversity of Lewis acidic sites, but also changed the adsorption of C = O groups, which lead to the increased aldol condensation activity of Cu/Al 2 O 3 . In conclusion, this study provides insight on the design of heterogeneous catalysts suitable for the solvent-free synthesis of aviation biofuel precursors from biomass-derived ketones.

Adsorption configuration↗
NASA NTRS1986

Integrated waste and water management system

The performance requirements of the NASA Space Station have prompted a reexamination of a previously developed integrated waste and water management system that used distillation and catalytic oxydation to purify waste water, and microbial digestion and incineration for waste solids disposal. This system successfully operated continuously for 206 days, for a 4-man equivalent load of urine, feces, wash water, condensate, and trash. Attention is given to synergisms that could be established with other life support systems, in the cases of thermal integration, design commonality, and novel technologies.

Murray, R. W.↗
DOE OSTI2020

Time-resolved in situ visualization of the structural response of zeolites during catalysis

Zeolites form an important class of materials that are widely used in various fields. Their unique properties come primarily from their size, shape, and connectivity of their sub-nm crystalline voids, the Si/Al ratio of the anionic framework, and the number and the nature of charge-balancing cations.The inhomogeneous distribution of the Si/Al ratio within crystals, and hence the cation density, the presence of organic residues, and their inhomogeneous distribution within crystals sensitively affect their performances because these factors influencethe intra-crystalline diffusion rates of the reactants and products. However, the information regarding these inhomogeneities in zeolite crystals cannot be obtained by conventional analytical tools because they only provide information regardingthe average properties of zeolite crystals. Here we employin situX-ray free electron laser-based time-resolved coherent X-ray diffraction imaging to investigate the internal deformations originating from the inhomogeneous Cu ion distributions in Cu-exchanged ZSM-5 zeolite crystals during the deoxygenation of nitrogen oxides with propene. We show that the interactions between the reactants and the active sites lead to an unusual strain distribution,which is confirmed by density functional theory simulations. Moreover, this elucidates the factors responsible for distinct active regions,which are essential to maximizing some applications with enhanced performances. These observations provide insights into the role of structural inhomogeneity in zeolites during a catalytic processand will assist the future design of zeolites for their applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding_the_deactivation_mechanisms_of_ethanol_conversion_over_Cu-Y_Beta_catalyst

Direct conversion of bioethanol to C₃⁺olefins is a promising pathway for sustainable aviation fuel (SAF) production, but catalyst deactivation limits long-term operation. The stability and deactivation mechanisms of multifunctional Cu–Y/Beta zeolite catalysts were investigated for ethanol-to-olefins conversion over 300 h time-on-stream in the presence of H2. Catalytic testing reveals progressive losses in ethanol conversion and C₃⁺ olefin selectivity accompanied by increased acetaldehyde formation. The catalyst testing studies correlate with a suite of characterizations of fresh, spent, and regenerated catalysts to identify the deactivation factors. The loss of Y Lewis acid sites is the primary deactivation element. Reversible acid site deactivation is caused by coke deposition, which blocks Y-derived Lewis acid sites responsible for aldol condensation, MPV reduction, and alcohol dehydration. Minor irreversible deactivation is observed and possibly results from hydrothermal dehydroxylation of Y–silanol interactions, resulting in permanent loss of Lewis acidity without zeolite framework degradation or Y aggregation. Cu sites undergo limited agglomeration into small nanoparticles but contribute insignificantly to catalyst deactivation, under the investigated time frame. Oxidative regeneration removes coke and redistributes Cu sites, leading to full recovery of the initial catalytic performance though the Y Lewis acid sites are unable to fully recover. These findings establish Lewis acid site degradation as the primary deactivation mechanism impacting long-term catalyst stability

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2017

Design Solutions for the Treatment of DMSD in the ISS Water Recovery System

Dimethylsilanediol (DMSD) has been identified as a problematic organic on ISS. This contaminant was initially identified in the Water Processor Assembly (WPA) product water in 2010 by the Total Organic Carbon Analyzer (TOCA). DMSD is not a crew health hazard at the levels observed in the product water, but it may degrade the performance of the Oxygen Generation System (OGS) which uses the WPA product water for electrolysis and does impact the effective operation of the WPA catalytic reactor. To mitigate these impacts, early replacement of the Multifiltration Beds in the WPA is required. An investigation has determined that the decomposition of atmospheric polydimethylsiloxanes (PDMSs) is the primary source of DMSD in the condensate. PDMSs are prevalent on ISS from a variety of sources, including crew hygiene products, adhesives, caulks, lubricants, and various nonmetallics. These PDMSs also contribute to degradation of the CHX hydrophilic coating, rendering it hydrophobic and therefore affecting its ability to transmit water to the condensate bus. In addition, literature research has determined that PDMSs are likely oxidized to DMSD in the atmosphere when exposed to hydroxyl radicals in the ISS atmosphere. To address these mechanisms, filters have been developed for removal of PDMSs from the ISS atmosphere. However, ongoing analysis indicates a significant reduction in atmospheric PDMSs is required to achieve a measurable reduction of DMSD in the condensate. As a result, additional measures are being pursued to mitigate this issue. First, credible sources are being investigated to quantity to the extent possible the significant sources of PDMSs and identify sources that can be reasonably removed from ISS. Second, a Reverse Osmosis technology is being investigated as an alternate means for removing DMSD from the condensate. This paper summarizes the current status of the overall effort to mitigate DMSD in the US condensate.

Perry, Jay↗
NASA NTRS1989

Neptune's Triton: A moon rich in dry ice and carbon

The encounter of the spacecraft Voyager 2 with Neptune and its large satellite Triton in August 1989 will provide a crucial test of ideas regarding the origin and chemical composition of the outer solar system. In this pre-encounter publication, the possibility is quantified that Titron is a captured moon which, like Pluto and Charon, originally condensed as a major planetesimal within the gas ring that was shed by the contracting protosolar cloud at Neptune's orbit. Ideas of supersonic convective turbulence are used to compute the gas pressure, temperature and rat of catalytic synthesis of CH4, CO2, and C(s) within the protosolar cloud, assuming that all C is initially present as CO. The calculations lead to a unique composition for Triton, Pluto, Charon: each body consists of, by mass, 18 1/2 percent solid CO2 ice, 4 percent graphite, 1/2 percent CH4 ice, 29 percent methanated water ice and 48 percent of anhydrous rock. This mix has a density consistent with that of the Pluto-Charon system and yields a predicted mean density for Triton of 2.20 + or - 0.5 g/cu cm, for satellite radius equal to 1,750 km.

Prentice, A. J. R.↗
DOE OSTI2023

Identification of 2-Hydroxyacyl-CoA Synthases with High Acyloin Condensation Activity for Orthogonal One-Carbon Bioconversion

One-carbon (C1) compounds are emerging as cost-effective and potentially carbon-negative feedstocks for biomanufacturing, which require efficient, versatile metabolic platforms for the synthesis of value-added products. Synthetic formyl-CoA elongation (FORCE) pathways allow diverse product synthesis from C1 compounds via iterative C1 elongation, operating independently from the host metabolism with reduced engineering complexity and improved theoretical yields. However, a major bottleneck was identified as the suboptimal kinetics of the core C1–C1 condensation enzyme, 2-hydroxyacyl-CoA synthase (HACS), catalyzing the acyloin condensation reaction between formaldehyde and formyl-CoA. Furthermore, we used a combinatorial approach of bioprospecting and rational protein engineering to identify multiple HACS variants with significantly improved activities toward C1 substrates. Sequence and structure alignment of the active variants elucidated the key regions for the catalytic function, which were targeted for mutagenesis, leading to improved catalytic efficiency. In parallel, a consecutive round of bioprospecting for homologs with high similarity with active variants revealed a highly active HACS variant exhibiting up to 7-fold improvement in catalytic efficiency (k cat /K M ) and 14-fold improvement in the FORCE pathway flux in vivo compared to the previous reports. Upon further optimization of the downstream pathway, the orthogonal C1-to-product bioconversion system showed a metabolic flux of up to 700 μM glycolate OD –1 h –1 (2.1 mmol gDCW –1 h –1 ) and an industrially relevant glycolate titer, rate, and yield of 5.2 g L –1 (67.8 mM), 0.22 g L –1 h –1 , and 94% carbon yield, respectively.

2-hydroxyacyl-CoA synthase↗
NASA NTRS1972

Study of the techniques feasible for food synthesis aboard a spacecraft

Synthesis of sugars by Ca(OH)2 catalyzed formaldehyde condensation (the formose reaction) has produced branched carbohydrates that do not occur in nature. The kinetics and mechanisms of the homogeneously catalyzed autocatalytic condensation were studied and analogies between homogeneous and heterogeneous rate laws have been found. Aldol condensations proceed simultaneously with Cannizzaro and crossed-Cannizzaro reactions and Lobry de Bruyn-Van Eckenstein rearrangements. The separate steps as well as the interactions of this highly complex reaction system were elucidated. The system exhibits instabilities, competitive catalytic, mass action, and equilibrium phenomena, complexing, and parallel and consecutive reactions. Specific finding that have been made on the problem will be of interest for synthesizing sugars, both for sustained space flight and for large scale food manufacture. A contribution to methodology for studying complex catalyzed reactions and to understanding control of reaction selectivity was a broad goal of the project.

Weiss, A. H.↗
NASA NTRS2017

Upgrades to the International Space Station Water Recovery System

The International Space Station (ISS) Water Recovery System (WRS) includes the Water Processor Assembly (WPA) and the Urine Processor Assembly (UPA). The WRS produces potable water from a combination of crew urine (first processed through the UPA), crew latent, and Sabatier product water. Though the WRS has performed well since operations began in November 2008, several modifications have been identified to improve the overall system performance. These modifications aim to reduce resupply and improve overall system reliability, which is beneficial for the ongoing ISS mission as well as for future NASA manned missions. The following paper details efforts to improve the WPA through the use of reverse osmosis membrane technology to reduce the resupply mass of the WPA Multi-filtration Bed and improved catalyst for the WPA Catalytic Reactor to reduce the operational temperature and pressure. For the UPA, this paper discusses progress on various concepts for improving the reliability of the system, including the implementation of a more reliable drive belt, improved methods for managing condensate in the stationary bowl of the Distillation Assembly, and evaluating upgrades to the UPA vacuum pump.

Kayatin, Matthew J.↗
NASA NTRS2017

Upgrades to the ISS Water Recovery System

The ISS Water Recovery System (WRS) includes the Water Processor Assembly (WPA) and the Urine Processor Assembly (UPA). The WRS produces potable water from a combination of crew urine (first processed through the UPA), crew latent, and Sabatier product water. Though the WRS has performed well since operations began in November 2008, several modifications have been identified to improve the overall system performance. These modifications can reduce resupply and improve overall system reliability, which is beneficial for the ongoing ISS mission as well as for future NASA manned missions. The following paper details efforts to improve the WPA through the use of Reverse Osmosis technology to reduce the resupply mass of the WPA Multifiltration Bed and improved catalyst for the WPA Catalytic Reactor to reduce the operational temperature and pressure. For the UPA, this paper discusses progress on various concepts for improving the reliability of the UPA, including the implementation of a more reliable drive belt, improved methods for managing condensate in the stationary bowl of the Distillation Assembly, deleting the Separator Plumbing Assembly, and evaluating upgrades to the UPA vacuum pump.

Kayatin, Matthew↗