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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Amphiphilic Block Copolymers for Flocculation and Hydrophobization of Legacy Waste Suspensions in Flotation Driven Dewatering Operations - 20162

Flotation has been effectively demonstrated as a low footprint, high efficiency separation process when utilising simple anionic surface modifying agents such as sodium dodecyl sulphate (SDS). These agents increase hydrophobicity to remove suspended cationic surface charged particulates such as Mg(OH){sub 2} from waste suspensions similar to those at British nuclear fuel management sites- where corrosion processes have degraded fuel cladding. The technology is advantageous as it could effectively be retrofitted into existing waste management facilities at nuclear waste management sites such Sellafield and Hanford as the simplicity (no moving parts) and size of this technology coupled with low cost of construction could be rapidly deployed to aid in risk and hazard reduction decommissioning operations with minimum impact to secondary waste generation. Previously, sodium dodecyl sulphate has been deployed as a collector agent to increase the hydrophobicity of Mg(OH){sub 2} suspended particles, achieving a maximum particulate extraction percentage of 93%. To achieve further particulate extraction, flotation performance has been determined to be a function of the hydrodynamic limitations extracting fine material (>20 μm). Fine particulates have been shown in the minerals industry to have an inability to overcome slipstreams created from rising bubbles in flotation cells, likely due to the low mass and thus momentum of the colloidal material, preventing interaction between the hydrophobized particles and air-water interfaces (bubbles). To combat this mass transfer resistance poly(acrylic acid)-block-poly(n-butyl acrylate) amphiphilic diblock copolymers were synthesised via reversible addition-fragmentation chain-transfer (RAFT) polymerisation. The anticipated mode of action of these polymers involves the hydrophilic poly(acrylic acid) block polymer acting as a flocculation agent to increase the mass of the aggregates, and the hydrophobic poly(n-butyl acrylate) modifies the hydrophobicity of the resulting flocs. The concentration of this polymer (termed a macro-collector) was varied and the change in particle size distribution of the particulate suspension was analysed using static light scattering. The flotation performance was then characterised by several methods including percentage particulate recovery, volume reduction factor and residual bulk particulate concentration. This was then benchmarked against the traditional surfactant collector agent SDS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

A Synchrotron-Based Vacuum Ultraviolet Photoionization Mass Spectrometer-Coupled Microreactor To Probe Thermocatalysis

Vacuum ultraviolet photoionization (VUV-PI) mass spectrometry offers an isomer-selective and universal ionization with minimal fragmentation detection of organics in complex chemical systems such as pyrolysis and combustion. Here, in this study, we report a state-of-the-art experimental setup of a universal catalytic microreactor combined with a molecular beam to investigate the thermocatalytic oxidation of a heterogeneous system relevant for probing reactions at gas–solid interfaces. In strong contrast to traditional off-line analytical methods, this technique is capable of identifying and quantifying short-lived species (radicals) as well as stable products to decipher initial reaction steps via the detection of nascent products. The thermocatalytic oxidative degradation of exo-tetrahydrodicyclopentadiene (JP-10), a high energy-density hydrocarbon fuel, over solid titanium–aluminum–boron reactive mixed metal nanopowder (Ti-Al-B RMNP) is exploited to showcase potential applications. Overall, some 59 nascent gas-phase products are identified via photoionization efficiency (PIE) curves, including oxygenated species and hydrocarbons comprising closed-shell molecules and radicals. The critical temperature for complete oxidative decomposition of JP-10 was lowered by 450 K from 1400 K to 950 K, indicating an efficient thermocatalytic action of Ti-Al-B nanoparticles on JP-10. The enabling of a universal chemical microreactor along with VUV-PI mass spectrometry broadens the applicability of this technique to hydrocarbon fuel oxidation and pyrolysis characterization. This isomer-selective sensitive probing along with the detection of radical transients makes the aforementioned technique superior to other conventional analytical techniques such as microflow tube and pyrolysis-gas chromatography coupled with mass spectrometry for investigating similar pyrolysis reactions and comprehensive quantification.

Paul, Dababrata [Univ. of Hawaii at Manoa, Honolul↗
DOE OSTI2022

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks

Cobaltocenium derivatives are promising components of the anion exchange membranes due to their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here we present an efficient modeling approach of assessing the chemical stability of substituted cobaltocenium CoCp 2 + based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp 2 + OH¯ complexes, whose dissociation is studied within the implicit solvent employing density functional theory. The data set of about 118 species based on 42 substituent groups characterized by a range of electron- donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron withdrawing-donating character of the substituents. Based on this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, are developed. Both models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 5.40% and average absolute errors less than 0.94 kcal/mol. The results show the potential of QNN to efficiently capture more complex relationships. Here, the concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the conventional regression analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Calculated covariance matrices for fission product yields using BeoH

Fission product yields (FPY) are important for a variety of applications (reactor neutronics, spent fuel, dosimetry, radiochemistry, etc.) and are currently included in many of the evaluated libraries around the world. The FPYs in the current US evaluation, ENDF/B-VIII.0, are mainly based on the 1994 evaluation of England and Rider and have only had slight updates—such as the inclusion of a 2 MeV point for 239 Pu—since their development. Additionally, only mean values and uncertainties are included in the evaluation, not full correlations. Los Alamos National Laboratory, in collaboration with several other institutes, has been working on an updated evaluation for the FPYs of 239 Pu(n,f), 235 U(n,f), 238 U(n,f), and 252 Cf(sf) using the deterministic, Hauser-Feshbach, fission fragment decay code, BeoH. BeoH calculates the FPYs consistently with many other prompt and delayed fission observables, explicitly taking into account multi-chance fission and ensuring consistency between observables. In addition to providing updated means and uncertainties for the FPYs on a pointwise energy grid from thermal to 20 MeV, we calculate correlations between all FPYs at each incident energy and across incident energies. Here, we discuss the development of these covariance matrices, differences in the correlations between FPYs based on the parameters that are included in the model optimization, and correlations across incident energies for neutron-induced fission.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

At-Line Sampling and Characterization of Pyrolytic Vapors from Biomass Feedstock Blends Using SPME-GC/MS-PCA: Influence of Char on Fast Pyrolysis

Solid-phase microextraction (SPME) coupled with GC-MS analysis was used for at-line sampling of pyrolytic vapors produced during fast pyrolysis of biomass. The pure and binary blends of switchgrass (SWG) and pine harvest residues (PT6) were used as feedstock. Sequential SPME sampling allowed for monitoring of changes in the pyrolysis vapors as char accumulated in the fluid bed. The concentration and composition of the vapors desorbed from the SPME fibers were investigated using GC-MS, and the data sets were then analyzed using principal component analysis (PCA) to compare the composition of the pyrolysis vapors over the course of the pyrolysis run. The chemical composition of both carbohydrate and lignin fragments varied as the char builds up in the reactor bed. Fragments derived from cellulose and xylan included anhydrosugars, furans and light oxygenated compounds. Lignin fragments included methoxyphenols, phenolic ketones and aldehydes, low molecular weight aromatics. The composition of the carbohydrate fragments changed more than the lignin fragments as the char build-up in the fluid bed. This combination of SPME-GC/MS-PCA were a novel, easy and effective method for measuring the composition and changes in the composition of pyrolysis vapors during the fast pyrolysis process. Here, this work also highlighted the effect of char build-up on the composition of the overall pyrolysis vapors.

09 BIOMASS FUELS↗
DOE OSTI2023

Photoexcitation of Fe 3 O Nodes in MOF Drives Water Oxidation at pH=1 When Ru Catalyst Is Present

Abstract Artificial photosynthesis strives to convert the energy of sunlight into sustainable, eco‐friendly solar fuels. However, systems with light‐driven water oxidation reaction (WOR) at pH=1 are rare. Broadly used [Ru(bpy) 3 ] 2+ (bpy=2,2’‐bipyridine) photosensitizer has a fixed +1.23 V potential which is insufficient to drive most water oxidation catalysts (WOCs) in acid, while Fe 2 O 3 , featuring the highly oxidizing holes, is not stable at low pH. Here, the key examples of Fe‐based metal–organic framework (MOF) water oxidation photoelectrocatalysts active at pH=1 are presented. Fe‐MIL‐126 and Fe MOF‐dcbpy structures were formed with 4,4’‐biphenyl dicarboxylate (bpdc), 2,2’‐bipyridine‐5,5’‐dicarboxylate (dcbpy) linkers and their mixtures. Presence of dcbpy linkers allows integration of metal‐based catalysts via coordination to 2,2’‐bipyridine fragments. Fe‐based MOFs were doped with Ru‐based precursors to achieve highly active MOFs bearing [Ru(bpy)(dcbpy)(H 2 O) 2 ] 2+ WOC. Materials were analyzed with X‐ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infra‐red (FTIR) spectroscopy, resonance Raman, X‐ray absorption spectroscopy, fs optical pump‐probe, electron paramagnetic resonance (EPR), diffuse reflectance and electric conductivity measurements and were modeled by band structure calculations. It is shown that under reaction conditions, Fe III and Ru III oxidation states are present, indicating rate‐limiting electron transfer in MOF. Fe 3 O nodes emerge as photosensitizers able to drive prolonged O 2 evolution in acid. Further developments are possible via MOF's linker modification for enhanced light absorption, electrical conductivity, reduced MOF solubility in acid, Ru‐WOC modification for faster WOC catalysis, or Ru‐WOC substitution to 3d metal‐based systems. The findings give further insight for development of light‐driven water splitting systems based on Earth‐abundant metals.

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

An attribution of the low single-scattering albedo of biomass burning aerosol over the southeastern Atlantic

Abstract. Aerosol over the remote southeastern Atlantic is some of the most sunlight-absorbing aerosol on the planet: the in situ free-tropospheric single-scattering albedo at the 530 nm wavelength (SSA530 nm) ranges from 0.83 to 0.89 within ORACLES (ObseRvations of Aerosols above CLouds and their intEractionS) aircraft flights from late August–September. Here we seek to explain the low SSA. The SSA depends strongly on the black carbon (BC) number fraction, which ranges from 0.15 to 0.4. Low organic aerosol (OA)-to-BC mass ratios of 8–14 and modified combustion efficiency values >0.975 point indirectly to the dry, flame-efficient combustion of primarily grass fuels, with back trajectories ending in the miombo woodlands of Angola. The youngest aerosol, aged 4–5 d since emission, occupied the top half of a 5 km thick plume sampled directly west of Angola with a vertically consistent BC:ΔCO (carbon monoxide) ratio, indicating a homogenization of the source emissions. The younger aerosol, transported more quickly off of the continent by stronger winds, overlaid older, slower-moving aerosol with a larger mean particle size and fraction of BC-containing particles. This is consistent with ongoing gas condensation and the coagulation of smaller non-BC particles upon the BC-containing particles. The particle volumes and OA:BC mass ratios of the older aerosol were smaller, attributed primarily to evaporation following fragmentation, instead of dilution or thermodynamics. The CLARIFY (CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017) aircraft campaign sampled aerosols that had traveled further to reach the more remote Ascension Island. CLARIFY reported higher BC number fractions, lower OA:BC mass ratios, and lower SSA yet larger mass absorption coefficients compared to this study's. Values from one ORACLES 2017 flight, held midway to Ascension Island, are intermediate, confirming the long-range changes. Overall the data are most consistent with continuing oxidation through fragmentation releasing aerosols that subsequently enter the gas phase, reducing the OA mass, rather than evaporation through dilution or thermodynamics. The data support the following best fit: SSA530nm=0.801+0055⋅(OA:BC) (r=0.84). The fires of southern Africa emit approximately one-third of the world's carbon; the emitted aerosols are distinct from other regional smoke emissions, and their composition needs to be represented appropriately to realistically depict regional aerosol radiative effects.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Gear Test Assembly - Experimental Testing and Analysis of Gears and Bearings - FY2026

The Gear Test Assembly (GTA) is an experimental test apparatus built and installed in the Mechanisms and Engineering Test Loop (METL) at Argonne National Laboratory (ANL). While designed to accommodate a variety of components intended for use in advanced compact in-vessel transfer machine, the focus of GTA been the testing of large radial spur gears. The performance of the components used in GTA motivates the choices made in the design, components, and material choices for the forthcoming METL test articles; the Gripper Test Assembly (GrTA), and the Bearing Test Assembly (BTA). To date, GTA has completed nine experimental testing campaigns and achieved over 21 million revolutions under prototypic sodium fast reactor loads and operating conditions. This report provides an overview and results for the two most recent experiments Campaign #8 and Campaign #9. `Campaign #8 was the first campaign to make use of a set of nickel alloy radial spur gears, made from Hastelloy C-22HS, and combined with heat-treated tapered roller bearings. The bearings and torque profile used allowed Campaign #8 to be directly compared with Campaign #1 where Inconel 718 gears were used instead. Campaign #8 attained 1,058,880 shaft revolutions within 23% of the 1,314,855 revolutions achieved in Campaign #1. These results demonstrate that the heat-treated tapered roller bearings show consistent increased lifetimes, approximately three times longer than for non heat-treated taper rollers, and that the particular material of the gear does not play a substantial role in performance. Similar to Campaign #7 where bearing failure resulted in fragmentation and transport of bearing material into the gear teeth led to tooth damage in the Inconel gears, a similar process led to the damage of the Hastelloy gears. Subsequent NDE analysis showed that the damage was only limited to the tooth surface and does not extend into the gear interiors. Based on the NDE reports, the Hastelloy gears can be reconditioned and put back into service for future campaigns as was done for the Inconel gears. Reconditioned Inconel 718 gears damaged in Campaign #7 were returned to service in Campaign #9 and paired with non heat-treated tapered roller bearings. In Campaign #9 a novel set of operating conditions were implemented whereby the gears and bearings were cycled between hot, submerged refueling conditions where fuel handling operations occurred and cold, dry, and inert conditions where the sodium was drained and the vessel was allowed to cool simulating long, ex-vessel storage of the fuel handling machine. A total of eight of these operating cycles were achieved before a bearing failure occurred after the accumulation of 475,692 shaft revolutions were achieved. During Campaign #9, one of the drive motors was damaged and over the course of a 240 day standby period, the entire GTA drive system was upgraded from a 480VAC system to a 240VAC system that provided the opportunity to consolidate wall-space in the METL facility and provide more space for additional test articles being installed in the coming year. The over 475,000 shaft revolutions achieved in Campaign #9 eclipses the previous record for lifetime of non heat-treated tapered roller bearings held by Campaign #3 of 392,000 shaft revolutions. Further analysis and future campaigns hope to shed light on the cause of this approximately 17% increase in lifetime.

42 ENGINEERING↗
DOE OSTI2021

Electrochemical Activation of C–C Bonds via Mediated Hydrogen Atom Transfer Reactions

Activating inert sp 3 -sp 3 carbon-carbon (C-C) bonds remains a major bottleneck in the chemical upcycling of recalcitrant polyolefin waste. Here, we use redox mediators to activate the inert C-C bonds. Specifically, we use N -hydroxyphthalimide (NHPI) as the redox mediator that is oxidized to phthalimide- N -oxyl (PINO) radical to initiate hydrogen atom transfer (HAT) reactions with benzylic C-H bonds. The resulting carbon radical is readily captured by molecular oxygen to form a peroxide that decomposes into oxygenated C-C bond-scission fragments. This indirect approach reduces the oxidation potential by > 1.2 V compared to the direct oxidation of the substrate. Studies with model compounds revealed the selectivity of C-C bond cleavage increases with decreasing C-C bond dissociation energy. With NHPI-mediated oxidation, oligomeric styrene ( M n = 510 Da, OS 510 ) and polystyrene (PS, ~10,000 Da) were converted into oxygenated monomers, dimers, and oligomers.

09 BIOMASS FUELS↗
DOE OSTI2025

Catalytic deconstruction of organic additive-containing plastics

Plastics waste ends up in landfills, oceans, and incinerators, posing major environmental and human health threats. Catalytic deconstruction is emerging as a key technological solution to handle complex plastics and has successfully converted virgin polymers into various products. Here, we investigate the resilience of chemical deconstruction technologies to organic additives, which are ubiquitous in plastics. We study catalyst-additive interactions experimentally and via first-principles calculations for plastics additives representative of entire classes. We reveal two deactivation mechanisms and demonstrate that many recently developed catalysts are inadequate for polyolefin conversion due to poisoning caused by the strong adsorption of most additives or their small fragments. Furthermore, we also identify conditions and catalysts that can circumvent the challenge of deconstruction in the presence of additives challenge.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Toward the Development of Molten Salt Reactor Diagnostics based on Resonantly Enhanced Laser Spectroscopy

One emerging concern within the safeguards community is how to best ensure compliance with nuclear security regulations within molten salt reactor (MSR) facilities. This problem is nontrivial as molten salts used for fuel or coolant are highly corrosive, chemically complex, and inherently require high operational temperatures. Laser spectroscopy methods such as laser-induced breakdown spectroscopy (LIBS) and laser-induced fluorescence (LIF) have previously been suggested for molten salt diagnostics due to their compatibility with liquid phase samples and potential for in-situ measurements [1]. In the former, the laser is used to ionize the sample, allowing for the characteristic light from electronic de-excitation as the resultant plasma cools to be used for material characterization. In the latter, a tunable light source is set be resonant with a specific transition, resulting in element specific excitation and the emission of fluorescence light. In our previous work [2], we demonstrated that LIF could be used for the detection of fission fragments such as Nd in solution through the separation of laser scatter and fluorescence within the time domain. Here, we present progress towards two alternate measurement schemes: LIF measurements based on spectroscopic discrimination of fluorescence emissions and resonant LIBS measurements that induce plasma using a light source set to the resonant frequency of a specific electronic transition. Both methods aim to exploit resonant excitation methods to enhance the emitted signal. The studies may provide routes for element-specific detection of constituents within complicated matrices and a means to better understand the chemical behavior of lanthanides and actinides relevant to MSRs.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗
DOE OSTI2021

Gas-Phase Stability of Large Lanthanide:Ligand Clusters Evaluated Using Collision-Induced Dissociation

Introduction In the reprocessing of f-elements present in used nuclear fuels, a variety of diglycolamides (DGA’s) are used as extractants for actinide partitioning. In particular, the Actinide-Lanthanide Separation (ALSEP) process typically utilizes either the N,N,N’,N’-tetraoctyl diglycolamide (TODGA) or N,N,N',N'-tetra-2-ethylhexyl diglycolamide (T2EHDGA) extractant ligands following the partitioning of uranium and plutonium from used nuclear fuel. To better understand fundamental interactions in these processes, covalent bonding of several f-elements with diglycolamides, primarily TODGA, is investigated in the gas phase using nanospray ionization and a quadrupole time-of-flight mass spectrometer. Further, analysis of the identity and relative strength of the cluster is enabled by MS2 isolation and collision induced dissociation. Methods Metal ion cluster analysis was completed using a Bruker (Billerica, MA, USA) mircOTOF-Q II quadrupole time-of-flight mass spectrometer with a CaptiveSpray nanospray ion source. Detection was accomplished using positive ionization mode. Metal: ligand solutions were assembled as 30 µM europium nitrate, samarium nitrate, cerium nitrate, or holmium nitrate and 3 µM DGA in acetonitrile or a 50:50 mixture of acetonitrile: isopropanol. Preliminary data The samarium cluster experiments yielded clusters with a samarium:TODGA ratio of up to 1:7 able to be isolated and evidence of greater ratios present in the mass spectrum. This is surprising, as metal clusters are not expected to have a coordination space able to accommodate this many TODGA ligands, due to its size and tridenticity. Collisional activation of [Sm(TODGA)3]3+ suggested loss of a TODGA radical cation, in addition to ligand fragmentation. In contrast, activation of clusters with higher Sm:TODGA ratios resulted in loss of entire ligands, with no evidence of fragmentation. A lower collision energy was required to remove ligands as the number of bound TODGAs increased, suggesting that in larger clusters, ligands are more delicately complexed to the metal. In addition, several clusters were observed with the composition [Sm(NO3)x(TODGA)n x]+3 x. With a single nitrate ion, clusters with up to six TODGAs were able to be isolated. In a similar pattern to the samarium clusters containing only TODGA, less collision energy was required to eliminate one or more TODGAs with increasing size. Clusters with composition [Sm(NO3)(TODGA)n-1]2+ appeared in lower abundance and were more collisionally stable than [Sm(TODGA)n]3+ clusters. With two nitrate ions, only clusters with a single TODGA were able to be isolated. Analogous europium experiments resulted in similar clusters. Ratios of up to 1:7 Eu:TODGA and clusters with one nitrate and up to five TODGAs were isolated. In clusters with two nitrate ions, only one or two TODGAs were observed to be bound. Similar to samarium, MS2 experiments with the Eu clusters suggested that larger clusters required less collision energy to eliminate TODGA. Europium clusters with the composition [Eu(NO3)(TODGA)n-1]2+ were observed in greater abundance and with greater stability than the equivalent cluster with the composition [Eu(TODGA)n]3+. Novel Aspect These are the first reported Ln:TODGA clusters, allowing us to begin to investigate intrinsic complexation of lanthanides with process-relevant ligands.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

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↗
DOE OSTI2022

High Activity and Selectivity for Catalytic Alkane–Alkene Transfer (De)hydrogenation by ( tBu PPP)Ir and the Importance of Choice of a Sacrificial Hydrogen Acceptor

The triphosphorus-coordinating pincer iridium fragment ( tBu PPP)Ir was recently reported to be highly active for the catalytic dehydrogenation of n-alkanes. Dehydrogenation is calculated to be highly regioselective for the terminal position of n-alkanes. Here, the extremely high intermolecular selectivity observed in n-alkane/cycloalkane competition experiments supports the prediction of extremely high regioselectivity for dehydrogenation of n-alkanes. The use of sterically unhindered hydrogen acceptors is key to observing the high activity of the ( tBu PPP)Ir fragment. 4,4-Dimethylpent-1-ene (TBP) is found to be particularly convenient for this purpose. With the commonly used hydrogen acceptor 3,3-dimethylbut-1-ene (TBE), ( tBu PPP)Ir affords n-alkane dehydrogenation at a rate no different than that obtained with the well-known fragment ( iPr PCP)Ir. However, with the use of TBP as acceptor, ( tBu PPP)Ir shows much greater activity for n-alkane transfer dehydrogenation than previously reported catalysts, affording appreciable rates even at 50 °C, an unprecedentedly low temperature for catalytic alkane transfer dehydrogenation. Also critical to the identification of ( tBu PPP)Ir as a highly effective catalyst is the use of n-alkane substrate rather than the commonly used “model” dehydrogenation substrate, cyclooctane, with which dehydrogenation rates are much lower than those with n-alkanes.

10 SYNTHETIC FUELS↗
DOE OSTI2022

13C-labeling reveals how membrane lipid components contribute to triacylglycerol accumulation in Chlamydomonas

Abstract Lipid metabolism in microalgae has attracted much interest due to potential utilization of lipids as feedstocks for biofuels, nutraceuticals, and other high-value compounds. Chlamydomonas reinhardtii is a model organism for characterizing the synthesis of the neutral lipid triacylglycerol (TAG), from which biodiesel is made. While much of TAG accumulation under N-deprivation is the result of de novo fatty acid (FA) synthesis, recent work has revealed that approximately one-third of FAs, especially polyunsaturated FAs (PUFAs), come from preexisting membrane lipids. Here, we used 13C-isotopic labeling and mass spectrometry to analyze the turnover of glycerol backbones, headgroups, FAs, whole molecules, and molecular fragments of individual lipids. About one-third of the glyceryl backbones in TAG are derived from preexisting membrane lipids, as are approximately one-third of FAs. The different moieties of the major galactolipids turn over synchronously, while the FAs of diacylglyceryltrimethylhomoserine (DGTS), the most abundant extraplastidial lipid, turn over independently of the rest of the molecule. The major plastidic lipid monogalactosyldiacylglycerol (MGDG), whose predominant species is 18:3α/16:4, was previously shown to be a major source of PUFAs for TAG synthesis. This study reveals that MGDG turns over as whole molecules, the 18:3α/16:4 species is present in both DAG and TAG, and the positional distribution of these PUFAs is identical in MGDG, DAG, and TAG. We conclude that headgroup removal with subsequent acylation is the mechanism by which the major MGDG species is converted to TAG during N-deprivation. This has noteworthy implications for engineering the composition of microalgal TAG for food, fuel, and other applications.

Plant Sciences↗
DOE OSTI2021

Synergistic Improvement of Carbohydrate and Lignin Processability by Biomimicking Biomass Processing

The sustainability and economic feasibility of modern biorefinery depend on the efficient processing of both carbohydrate and lignin fractions for value-added products. By mimicking the biomass degradation process in white-rote fungi, a tailored two-step fractionation process was developed to maximize the sugar release from switchgrass biomass and to optimize the lignin processability for bioconversion. Biomimicking biomass processing using Formic Acid: Fenton: Organosolv (F 2 O) and achieved high processability for both carbohydrate and lignin. Specifically, switchgrass pretreated by the F 2 O process had 99.6% of the theoretical yield for glucose release. The fractionated lignin was also readily processable by fermentation via Rhodococcus opacus PD630 with a lipid yield of 1.16 g/L. Scanning electron microscope analysis confirmed the fragmentation of switchgrass fiber and the cell wall deconstruction by the F 2 O process. 2D-HSQC NMR further revealed the cleavage of aryl ether linkages (β-O-4) in lignin components. These results revealed the mechanisms for efficient sugar release and lignin bioconversion. The F 2 O process demonstrated effective mimicking of natural biomass utilization system and paved a new path for improving the lignin and carbohydrate processability in next generation lignocellulosic biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2021

Identification and quantification of lignin monomers and oligomers from reductive catalytic fractionation of pine wood with GC × GC – FID/MS

Thorough lignin characterization is vital to understand the physicochemical properties of lignin and to evaluate lignocellulose biorefinery processes. In this study, an in-depth characterization of lignin oil, obtained from reductive catalytic fractionation (RCF) of pine wood, was performed with quantitative GC × GC – FID analysis and qualitative GC × GC – MS. By utilizing high-temperature resistant column sets in the GC × GC system and by applying a derivatization step, unambiguous detection of lignin monomers, dimers, and trimers is enabled. In addition to confirm the identity of eleven monomers, corresponding to 34 wt% of the RCF lignin oil, thirty-six dimers (16 wt%) and twenty-one trimers (7 wt%) were comprehensively identified by analysis of their mass spectra and quantified by a FID, encompassing the identity of an additional 23 wt% of the RCF lignin oil. The proposed structures reveal the interlinkages present in the dimeric and trimeric oligomers, containing β-5, β-1, β–β, 5–5, and a minor fraction of β-O-4 and 4-O-5 bonds. Furthermore, aliphatic end-units in the dimeric and trimeric molecules were identified, consisting of various substituents at the C4 position, that have been previously observed in the RCF-derived lignin monomers. To reduce complexity for analysis, the RCF oil was separated into six fractions, prior to analysis. The structural motifs (inter-unit linkages and end-units) that are found in the different fractions vary significantly, such that the lignin fractions extracted in more polar solvents contained higher molecular weight fragments and more hydroxyl containing structural motifs. Additionally, the identified structures of individual dimer and trimer molecules by GC × GC align well with and further complement the recent findings from 1 H– 13 C HSQC NMR spectroscopy, demonstrating complementarity between both 2D techniques to obtain a holistic view on both the molecular structures and the distribution of bonds and end-units in RCF oil. The combination of these two techniques provides a powerful tool for future RCF and other lignin depolymerization research.

09 BIOMASS FUELS↗
DOE OSTI2025

Fe‐Triazolate Metal–Organic Frameworks as Water Oxidation Catalysts with Dual Photoanode Functionality

Artificial photosynthesis is an emerging technology that achieves renewable fuels, such as hydrogen, from sunlight. Its realization depends on finding highly active and stable catalysts of water splitting and photoactive materials for light absorption. To be scalable, these should contain only abundant elements. Here, for the first time, Fe-triazolate (Fe(ta) 2 ) and its metal substituted derivatives (Fe-Metal(ta) 2 ) Metal-organic frameworks (MOFs) are characterized as new dual-function materials for photo-absorption and water oxidation catalysis in acidic media. The materials were studied by a range of structural, spectroscopic, and computational density functional theory (DFT) techniques. Fe(ta) 2 and Fe-Mn(ta) 2 were found to be highly active and stable in chemical and photochemical water oxidation, and in addition function as photoanodes, with photo-electrocatalytic currents (∼2.00 x 10 −3 Acm −2 at + 1.4 V vs. Ag/AgCl) at pH = 1. The possibility of a unique catalytic mechanism where O─O bond formation is possible from the coupling of two adjacent Fe IV = O fragments was demonstrated by DFT analysis. Thus, Fe-triazolate MOF has been established as a new, stable, scalable, versatile, and efficient platform for sustainable energy conversion in the realm of artificial photosynthesis.

Artificial photosynthesis↗