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DOE OSTI2022

Role of side-chain length on gas transport of CO 2 /CH 4 mixtures in polymers with side-chain porosity

Polymers of intrinsic microporosity (PIMs) are traditionally formed from ladder backbones, but recent synthetic advances have allowed for the formation of non-traditional PIMs using a poly(ladder) motif, whereby rigid PIM-like sidechains are appended onto more flexible backbones. The effect of side-chain length on free volume and gas transport properties was recently evaluated for a methoxy-functionalized poly(ladder) (OMe-ROMP). In this study, we elaborate on the role of side-chain length and its influence on mixed-gas performance and plasticization stability for OMe-ROMP. Pure-gas sorption results are also reported, including hysteresis effects from CO 2 conditioning. Taken together, this study reveals the role of side-chain length on gas sorption, diffusion, and plasticization for CO 2 /CH 4 separations. Finally, we conclude that the length of a rigid side chain in the poly(ladder) motif is a valuable structural parameter to control sorption, diffusion, and stability towards plasticization for gas separation membrane materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on a Hanford AP Tank Farm Primary Exhauster Slipstream

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2025

Novel Electrochemical Technique: Serial Open Circuit Potentiometry to Examine the Separability of Lanthanides in Molten Salts

The accumulation of lanthanide fission products in molten salts reduces the efficiency of pyroprocessing used nuclear fuel. Lanthanide fission products are notoriously difficult to separate due to their similar physical and electrical properties. We developed a novel electrochemical technique called serial open circuit potentiometry (SOCP) which allows us to delineate between metal deposition reactions with similar reduction potentials to great precision. SOCP has several advantages over traditional open circuit potentiometry including its ability to create 3D plots that describe all metal deposition reactions in a system. This information can be used to precisely determine equilibrium potentials of metal deposition reactions and quantify their error, determine nucleation potentials, and determine the nucleation and growth mechanism. In this work, we demonstrated the effectiveness of SOCP by studying molten salt mixtures containing CeCl3, GdCl3, and both CeCl3 and GdCl3 in LiCl-KCl eutectic.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on the 702-AZ Primary Exhauster for the Hanford AY/AZ Tank Farms during a Waste-Disturbing Event

Washington River Protection Solutions (WRPS) conducted tests using two types of chemical cartridges for use in air-purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance1 for APRs used to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPC) from vapors exiting the 702-AZ Primary Exhauster for the Hanford AY-AZ tank farms. Unlike prior cartridge testing on the 702-AZ Primary Exhauster, the recent tests were performed during a waste-disturbing event. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedules. Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate the cartridge service life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted from February 10–11, 2017, on a slipstream from the 702-AZ exhauster fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1 (SCOTT Safety, Monroe, North Carolina), were assessed on separate days. Sample media (sorbent tubes) and canisters (e.g., Summa) sampling were used to collect samples of the vapor stream entering and exiting the respirator cartridge and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Simulation and Optimization of Volatile Fatty Acid Upgrading Strategies for Sustainable Transportation Fuel Production

Underutilized wet waste is a promising feedstock for production of carbon-neutral or carbon-negative liquid transportation fuels. Arrested methanogenesis of wet wastes by microbes, which produces mixtures of C2-C8 carboxylic acids (volatile fatty acids, VFAs), is practiced industrially at a pilot scale and the VFA products can be catalytically upgraded to molecules suitable for use as transportation fuels (alcohols and alkanes) via sequential ketonization and hydrogenation, both steps of which have been demonstrated with high (>90%) yield at the lab scale. We present in this work a simulation-based decision-making framework which evaluates upgrading strategies of VFAs to alcohol- and hydrocarbon-based neat and blended diesel, jet, and gasoline fuels. The processes utilize sequential upgrading steps (ketonization and hydrogenation) accompanied by one distillation step (either separating VFAs before ketonization or alcohols after ketone hydrogenation) to form two liquid streams: a light alcohol stream best suited as a light-duty fuel and a heavy alcohol or hydrocarbon stream best suited as a diesel or jet fuel. Suitability of the liquid products as transportation fuels and maximum blending levels with petrofuels comes from simulation of critical fuel properties (boiling point, flash point, lower heating value, viscosity, melting point, water solubility, and cetane/octane number). Catalytic upgrading steps and fuel property mixing models used by the simulation are experimentally validated. We demonstrate the flexibility of the decision-making algorithm by evaluating processing scenarios for experimentally-observed VFA profiles with varied carbon chain length distributions. Processing scenarios are optimized for either maximum total renewable carbon utilization or production of heavy-duty (jet or diesel) fuels. We evaluate the economic viability and CO2 emissions of each proposed upgrading scenario using techno-economic and life cycle analyses. The decision-making framework developed in this work can also be used to down-select promising strategies for upgrading of other bio-based feedstocks to sustainable fuels and chemicals.

aviation fuel↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on a Hanford AN Tank Farm Exhauster Slipstream

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air purifying respirators to determine the period of time that the cartridges would provide adequate performance to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPCs) from vapors exiting the exhauster at the Hanford AN tank farm. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing cartridge change schedule. Testing is commonly applied in situations where mixtures of COPCs exist and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted from September 30−October 2, 2016, on a slipstream from the AN Exhauster under static conditions fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1 (SCOTT Safety, Monroe, North Carolina) were assessed on separate days. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on the 702-AZ Primary Exhauster for the Hanford AY/AZ Tank Farms

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air purifying respirators to determine the period of time that the cartridges would provide adequate performance to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPC) from vapors exiting the 702-AZ primary exhauster for the Hanford AY/AZ tank farms. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing cartridge change schedules. Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted from August 26–28, 2016, on a slipstream from the 702-AZ exhauster, under static conditions fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1(SCOTT Safety, Monroe, North Carolina) were assessed on separate days. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge, and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and change-out frequency.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on a Hanford AW Tank Farm Exhauster Slipstream

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air-purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance for APRs used to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPCs) from vapors exiting the exhauster for the Hanford AW tank farm. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedules. Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service-life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted from September 23-25, 2016, on a slipstream from the AW exhauster, under static conditions fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1 (SCOTT Safety, Monroe, North Carolina), were assessed on separate days. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge, and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on a Hanford Tank SY-102

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air-purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance1 for APRs used to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPC) from vapors emanating from the headspace of tank SY-102 on the Hanford Site. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedule. Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, worker breathing rate, and cartridge adsorption capacity. Testing was conducted from July 8–10, 2016, on headspace vapors from Hanford tank SY-102 under static conditions2 fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1 (SCOTT Safety, Monroe, North Carolina) were assessed on separate days. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life.

42 ENGINEERING↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on a Hanford Tank SY-102

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air-purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance for APRs used to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPC) from vapors emanating from the headspace of tank SY-102 on the Hanford Site. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedule. Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to assure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, worker breathing rate, and cartridge adsorption capacity. Testing was conducted from July 8–10, 2016, on headspace vapors from Hanford tank SY-102 under static conditions fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and SCOTT 7422-SC1 (SCOTT Safety, Monroe, North Carolina) were assessed on separate days. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2024

Exploring the Nature of f-Element Soft Donor Interactions Using Electronically Tunable Azolate Ionic Liquids

This project was undertaken to advance the understanding of how f-elements interact with moderately soft donors, a heavily investigated yet open question which is of prime importance in spent nuclear fuel processing and fundamental inorganic chemistry. During the course of the project, based on exciting results, a stretch goal was developed to study the hydrolysis products of transuranic actinide metals, a somewhat understudied field even with its significance in nuclear fuel cycle and impacts in environmental chemistry. The stretch goal was to take our serendipitous discovery of an easy route to isolation of crystalline multinuclear ƒ-element hydrolysis products, and apply it to gaining a mechanistic understanding of Pu(III/IV) colloid formation. The simplicity of our techniques should lend themselves to the remote handling required for study of many transuranic elements. We developed several methodologies using azolium azolate chemistry to overcome ƒ-element hydrolysis problems that prohibit the isolation of ƒ-element soft donor complexes and to build a crystallographic library of ƒ-element N-donor complexes as a means to understand the fundamental differences between actinide and lanthanide interactions with moderately soft donor ligands. Our next major endeavor will be to transfer this chemistry from 4ƒ elements to transuranic elements, particularly in the study of hydrolysis of Pu(III/IV). While our work is fundamental in nature, applications of the knowledge we are generating should be felt in such diverse fields as catalysis, separations in general, nuclear waste remediation specifically, and many other applications in f-element magnetic and luminescent properties. The potential ramifications of the consistent and robust formation of hydrolysis controlled hexanuclear lanthanide structures are enormous, with future uses being catalyst formation, higher-nuclearity structure synthesis using our hexanuclear motif as a fundamental building block, Pu waste remediation, separations, and many other potential applications resulting from characteristic magnetic and luminescent properties of lanthanide polynuclear structures. Three synthetic methodologies (direct mixing with variable stoichiometries, use of volatile solvent, metathesis) were developed starting with 7 acidic and 6 basic azoles to obtain ionic liquids suitable for f-element coordination. Proton transfer by acidic/basic azole combination led to suitable low melting salts and two cocrystals. Acid/base reaction of azoles with soft-donor permanent cations of ([X 4444 ][OH] (where [X 4444 ] + = tetrabutylammonium [N 4444 ] + or tetrabutylphosphonium [P 4444 ] + ) with weakly acidic azoles including imidazole, 1,2,3-triazole, 1,2,4-triazole, 5-aminotetrazole, 4,5-dicyanoimidazole, and 2-amino-4,5-dicyanoimidazole) revealed several suitable low-melting salts. Metathesis reactions of Na(azolate) were conducted by first using weakly acidic azoles including 4,5-dicyanoimidazole, 2-amino-4,5-dicyanoimidazole, 5-aminotetrazole, and 1,2,4-triazole to form sodium or lithium salts using group(I) hydroxides in methanolic solutions. The best results were obtained by reacting the basic and acidic azoles directly in 1:1 or 3:1 ratios at elevated temperatures. Twenty-two azole mixtures were identified which are either low melting solids or room temperature liquids. Each of the low melting solids was confirmed to be a new solid phase, each of which is being further characterized. The liquids and solids are anticipated to be ILs, eutectics, or partially ionized systems, all of which will be suitable for the dissolution of f-element salts. Five new synthetic methodologies were developed to finding suitable crystallization conditions for f-element complexation with the goal of finding simple one pot reaction syntheses and crystallization strategies that could be used under the demanding conditions of transuranic chemistries. These synthetic methods yield many new crystalline phases which were studied by single crystal X-ray diffraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2025

Bayesian calibration of bubble size dynamics applied to CO 2 gas fermenters

To accelerate the scale-up of gaseous CO 2 fermentation reactors, computational models need to predict gas-to-liquid mass transfer which requires capturing the bubble size dynamics, i.e. bubble breakup and coalescence. However, the applicability of existing models beyond air–water mixtures remains to be established. Here, an inverse modeling approach, accelerated with a neural network surrogate, calibrates the breakup and coalescence closure models, that are used in class methods for population balance modeling (PBM). The calibration is performed based on experimental results obtained in a CO 2 -air–water-coflowing bubble column reactor. Bayesian inference is used to account for noise in the experimental dataset and bias in the simulation results. To accurately capture gas holdup and interphase mass transfer, the results show that the breakage rate needs to be increased by one order of magnitude. In conclusion, the inferred model parameters are then used on a separate configuration and shown to also improve bubble size distribution predictions.

09 BIOMASS FUELS↗

DOE OSTI2023

Near Quantitative Removal of Selenate and Sulfate Anions from Wastewaters by Cocrystallization with Chelating Hydrogen-Bonding Guanidinium Ligands

Selenium (Se) has become an environmental contaminant of aquatic ecosystems as a result of human activities, particularly mining, fossil fuel combustion, and agricultural activities. By leveraging the high sulfate concentrations relative to Se oxyanions (i.e., SeO n 2– , n = 3, 4) present in some wastewaters, we have developed an efficient approach to Se-oxyanion removal by cocrystallization with bisiminoguanidinium (BIG) ligands that form crystalline sulfate/selenate solid solutions. The crystallization of the sulfate, selenate and selenite, oxyanions and of sulfate/selenate mixtures with five candidate BIG ligands are reported along with the thermodynamics of crystallization and aqueous solubilities. Oxyanion removal experiments with the top two performing candidate ligands show a near quantitative removal (>99%) of sulfate or selenate from solution. When both sulfate and selenate are present, there is near quantitative removal (>99%) of selenate, down to sub-ppb Se levels, with no discrimination between the two oxyanions during cocrystallization. Reducing the selenate concentrations by 3 orders of magnitude or more relative to sulfate, as found in many wastewaters, led to no measurable loss in Se removal efficiencies. This work offers a simple and effective alternative to selective separation of trace amounts of highly toxic selenate oxyanions from wastewaters, to meet stringent regulatory discharge limits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Analysis of Respirator Cartridge Performance Testing on Hanford Tank A-101

Washington River Protection Solutions (WRPS) conducted tests on two types of chemical cartridges for use in air purifying respirators (APR) to determine the period of time that the cartridges would provide adequate performance1 to protect workers when exposed to a mixture of Chemicals of Potential Concern (COPCs) from vapors emanating from the headspace of tank A-101 on the Hanford Site. The Occupational Safety and Health Administration (OSHA) identifies cartridge testing as a valid approach for establishing a cartridge change schedules.[3] Testing is commonly applied in situations where mixtures of COPCs exist, and where other approaches, such as manufacturer recommendations and modeling, are less reliable. The tests were designed and conducted to ensure measurement and/or control of the key variables OSHA identified as important to estimate cartridge service life, including temperature, humidity, COPC concentration, breathing rate, and cartridge adsorption capacity. Testing was conducted over a period from July 22-24, 2016, using headspace vapors from Hanford tank A-101 under static conditions2 fed to a respirator cartridge test stand developed by WRPS in collaboration with HiLine Engineering (Richland, Washington). Multipurpose respirator cartridges, SCOTT 7422-SD1 and 7422-SC1 (SCOTT Safety, Monroe, North Carolina) were assessed on separate days with A-101 headspace vapors. Sample media (sorbent tubes) were used to collect samples of the vapor stream entering and exiting the respirator cartridge, and were subsequently analyzed for COPC concentrations. Pacific Northwest National Laboratory was tasked with conducting an independent analysis of the analytical results and making recommendations based on the results for respiratory cartridge performance and service life. Key conclusions from the assessment of the 59 COPCs in this study are described below: • Based on d measured cartridge inlet vapor concentrations from tank A-101 headspace, both ammonia and N-Nitrosodimethylamine (NDMA) exceeded their Occupational Exposure Limits (OEL).3 These measurements were generally consistent with maximum A-101 headspace measurements previously obtained for these two compounds. • Ammonia had respirator cartridge outlet concentrations that exceeded 10% of the OEL for both cartridges tested, indicating breakthrough for each. For the SCOTT 7422-SD1 cartridge, ammonia appeared to breakthrough above 10% of its OEL after 2 hours. For the SCOTT 7422-SC1 cartridge, ammonia breakthrough appeared to occur after 8 hours. 1 “Adequate performance” refers to the breakthrough criteria used in this analysis—that is, sustained cartridge outlet concentrations above 10% of the OEL. For some COPCs, an alternate threshold has been applied when necessary due to higher detection limit (DL)/reporting limit (RL) values for specific compounds. Ultimately, Industrial Hygiene professionals will use these results along with specific hazard assessments to determine service life and cartridge use that provides the necessary performance. 2 These tests were conducted under static conditions absent waste-disturbing activities in the subject tank or tank farm. 3 Occupational Exposure Limits accepted for Hanford Tank Farm use are based on OELs established by a U.S. governmental agency or national professional organization (e.g., OSHA, National Institute for Occupational Safety and Health, American Conference of Governmental Industrial Hygienists), or if no U.S. OEL exists, standard toxicological practices are applied to develop OELs using non-U.S. exposure limits, other established OELs for chemical surrogates when available, or other standard procedures. The OEL for NDMA was established in 2005 based on the MAK (Maximale Arbeitsplatzkonzentration) Commission standard adopted in Europe. iv • Despite respirator inlet measurements for NDMA that were in excess of its OEL, all corresponding outlet measurements, from both respirator cartridges, were below analytical DL 1 for the

61 RADIATION PROTECTION AND DOSIMETRY↗

DOE OSTI2022

A Water-Resistant Hydrogen-Bonded Organic Framework for Ethane/Ethylene Separation in Humid Environments

The separation of ethane (C 2 H 6 ) and ethylene (C 2 H 4 ) represents a crucial process for the production of polymer-grade C 2 H 4 , and adsorptive separation holds enormous promise for this industrially important but challenging task. Furthermore we report a new hydrogen-bonded organic frameworks (HIAM-102) with suitable channel and superhydrophobicity for preferential adsorption of C 2 H 6 over C 2 H 4 . HIAM-102 shows a C 2 H 6 /C 2 H 4 IAST selectivity of 1.9 and C 2 H 6 uptake of 48.25 cm 3 /g at 1 bar and 298 K. Benefitted from the hydrophobic pore surface, it can well-separate C 2 H 6 and C 2 H 4 under highly humid conditions as confirmed by experimental column breakthrough measurements. Computational calculations provide additional support for the experimental observations that the nonpolar channel of HIAM-102 interact favorably with C 2 H 6 over C 2 H 4 .

36 MATERIALS SCIENCE↗

DOE OSTI2025

Interplay between Mixed and Pure Exciton States Controls Singlet Fission in Rubrene Single Crystals

Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of separated triplet excitons T. SF is widely studied as it may help overcome the Shockley−Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast time scales of the SF process. Here, we apply 14 fs-1 ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. Our data demonstrates that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S/TT], which rapidly (<100 fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S/TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and offer alternative strategies for the development of SF-enhanced photovoltaic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Changes in rock matrix compressibility during deep CO 2 storage

Geologic carbon storage projects aim to permanently trap large volumes of CO 2 in reservoir rock sealed with low permeability layers. As high-pressure supercritical or liquid CO 2 is injected, hydromechanical and chemical processes caused by the reaction between the rock and acidic mixture of brine and CO 2 are initiated. The compressibility of reservoir rock needs to be properly characterized in order to assess the deformation and stability of the host formations, and there are a number of factors to be considered, including the matrix structure, solid, pores, and fluid. Here this study triggers from a fundamental question whether CO 2 treatment affects the compressibility of the rock matrix and its dominant composing solid minerals. Three different reservoir representatives are selected: Berea sandstone for silica-rich rock, and Apulian limestone and Indiana limestone for calcite-rich rock. Quartz and calcite are the main composing minerals of the reservoir rock, and their crystals are separately examined. Experimental methods are introduced for high-pressure CO 2 treatment of water-saturated materials, and measurements of the unjacketed and solid compressibilities are conducted. No change in the solid compressibility of the sandstone and quartz after CO 2 treatment is observed, whereas it increases by 18–21% for the limestones and by 15% for calcite. The latter observation is inconsistent with the ultrasonic wave velocities measurements and is believed to be due to the local dissolution of the calcite crystal surface. Our results show that only the solid matrix of the limestones becomes more compressible after CO 2 treatment. Consequent microimaging and mercury intrusion porosimetry analyses allowed observations of dissolution and precipitation of calcite, and creation of new connected and non-connected pores. Finally, the changes in limestone solid compressibilities and pore structure could significantly affect the rock properties and behavior during and after CO 2 injection and should be accounted for in the reservoir models.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2023

Development of a Structure for Lossless Ion Manipulations (SLIM) High Charge Capacity Array of Traps

Enhancing the sensitivity of low abundance ions in a complex mixture without sacrificing experiment throughput is highly desirable. This work demonstrates a way to greatly improve the sensitivity of ion mobility (IM) selected ions by accumulating them in an array of high-capacity ion traps located inside a novel structures for lossless ion manipulations ion mobility spectrometer (SLIM-IMS) module. The array of ion traps used in this work consisted of seven independently controllable traps. Each trap was 386 mm long and possessed a charge capacity of ~4.5×10 8 charges, with a linear range extending to ~2.5×10 8 charges. Each ion trap could be used to extract a peak (or ions over a mobility range) from an ion mobility separation based on arrival time. Ions could be stored without losses for long times (>100 s) and then released all at once or one trap at a time. It was possible to accumulate large ion populations by extracting and storing ions over repeated IM separations. We report enrichment of up to seven individual ion distributions could be performed using the seven independently controllable ion traps. Additionally, the ion trapping process effectively compressed ion populations into narrow peaks, which provides a greatly improved basis for subsequent ion manipulations. The array of high charge-capacity ion traps provides a flexible addition to SLIM and a powerful tool for IMS-MS applications requiring high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗