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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Synthesis of Actinide Materials for the Study of Basic Actinide Science and Rapid Separation of Fission Products

This dissertation covers several distinct projects relating to the fields of nuclear forensics and basic actinide science. Post-detonation nuclear forensics, in particular, the study of fission products resulting from a nuclear device to determine device attributes and information, often depends on the comparison of fission products to a library of known ratios. The expansion of this library is imperative as technology advances. Rapid separation of fission products from a target material, without the need to dissolve the target, is an important technique to develop to improve the library and provide a means to develop samples and standards for testing separations. Several materials were studied as a proof-of-concept that fission products can be extracted from a solid target, including microparticulate (< 10 μm diameter) dUO 2 , porous metal organic frameworks (MOFs) synthesized from depleted uranium (dU), and other organicbased frameworks containing dU. The targets were irradiated with fast neutrons from one of two different neutron sources, contacted with dilute acids to facilitate the separation of fission products, and analyzed via gamma spectroscopy for separation yields. The results indicate that smaller particle sizes of dUO 2 in contact with the secondary matrix KBr yield higher separation yields than particles without a secondary matrix. It was also discovered that using 0.1 M HNO 3 as a contact acid leads to the dissolution of the target material. Lower concentrations of acid were used for future experiments. In the case of the MOFs, a larger pore size in the framework leads to higher separation yields when contacted with 0.01 M HNO 3 . Different types of frameworks also yield different results.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Atomically Precise Membranes for the Separation of Gases

Industrial separations require enormous amounts of energy, accounting for approximately half the industrial energy use and 10–15% of the total energy consumption. Distillation alone accounts for about half the energy demand for industrial separations. If these processes could be replaced by an energy-efficient membrane separation process, this energy demand could be reduced by 90%. However, although some membrane processes have made inroads into thermal distillation, for membrane-based separations to replace the distillation process to a far more significant and practical level, new membranes with higher robustness, selectivity, and flux still need be developed. In this membrane development program, we leveraged Temple University’s prior work in spiroligomers to develop robust membrane structures. These structures can be formed into atomically precise pores by controlling the chemical synthesis and the oligomer building blocks to first build precisely controlled macrocycles and then subsequently crosslinking these macrocycles to produce a membrane. Furthermore, through the highly controllable chemistry of our molecular building blocks, not only can we integrate pores with highly controllable and reproducible size and morphology, but we can also target internal functionalization. By using a range of scalable membrane synthesis approaches, combined with control of each and every pores internal chemistry and molecular conformation we can achieve membrane structures that can display the ultimate in high selectivity and permeance. The Mainstream-Temple University membranes can be designed to achieve ultra-selective separations based on the key factors of molecular size, shape, and functionality. In our approach to fabricate scalable atomically precise membranes, we used our molecular Lego nanostructures. We demonstrated an approach to create atomically precise pores within the membrane with pores that are the dimensions of the molecule we are trying to separate. Moreover, in addition to controlling the morphology of the membrane structure by controlling the size of every pore, we can also decorate every pore with precisely targeted and placed functional groups. These accurately placed functional groups can provide selective binding to molecules and provide enhanced selectivity via a facilitated transport mechanism. In Phase II, the Mainstream-Temple University team demonstrated the scalable synthesis of oligomers and the ability to control the pore internal and external functionality, or chemistry, to allow the fabrication of a thin-film membrane. The initial steps of the spiroligomer synthesis to produce the two key bis-amino enantiomer building blocks were scaled from the gram scale to the kilogram scale, obtaining 25 kg of the materials by transferring the procedure to a toll manufacturer. Finally, we successfully optimized the fabrication of these macrocycles into robust membranes. We successfully transitioned from a laboratory based, hard-to-scale Langmuir trough synthesis to a highly scalable, roll-to-roll applicable, interfacial polymerization process. During this Phase II program, we established a platform of atomically precise membranes where our highly controllable, atomically precise macrocycles served as a scaffold with precisely and uniformly controlled pores. Furthermore, this layer can be tailored to accommodate a diverse range of functional groups, which both further controlled the pore size to enhance the sieving effect as well as imparting precisely controlled targeted selectivity through biomimetic molecular interactions. In this Phase II, we established and scaled up a platform approach to both tune the pore size and chemistry as well as scale it to produce membranes that can be applied to a wide range of industries. In future development, the project team expects to scale up both the macrocycle building block production and interfacial polymerization process to produce the atomically precise membrane with targeted pore sizes and pore chemistries.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Development of Carbon Molecular Sieves Hollow Fiber Membranes based on Polybenzimidazole Doped with Polyprotic Acids with Superior H 2 /CO 2 Separation Properties (Final Report)

The goal of this project was to develop a highly efficient membrane-based process to capture CO 2 from coal-derived syngas with 95% CO 2 purity, achieving the cost of electricity (COE) 30% below the baseline capture approaches (i.e., Selexol process) when coupled with the advancement in other areas of the power generation facility. Our core approach is based on high-permeance hollow fiber membranes (HFMs) with superior H 2 /CO 2 separation properties at the syngas process conditions, which can then be further utilized to design membrane reactors for process intensification of H 2 production and purification and CO 2 capture. Three organizations with complementary skills collaborated to achieve the goal, including the University at Buffalo (UB), Los Alamos National Laboratory (LANL), and Trimeric Corporation (Trimeric). We formulated logical steps to bring the membrane technology from Technology Readiness Level (TRL) 3 (Experimental proof of concept) to TRL 4 (Laboratory scale validation in relevant environment). During the budget period (BP) 1, we screened various polymeric materials and identified polybenzimidazole doped with inorganic polyprotic acids as the desirable platform. The acid doping increases the H 2 /CO 2 selectivity, and the sequential carbonization increases H 2 permeability while retaining the high selectivity. By manipulating the acid type and doping level and the carbonization temperature, we demonstrated advanced carbon molecular sieving (CMS) materials with H 2 permeability of above 200 Barrer (1 Barrer = 10 -10 cm 3 (STP) cm cm -2 s -2 cmHg -1 ) and H 2 /CO 2 selectivity of above 40 at 200-300°C with simulated syngas containing CO and water vapor. For example, the PBI-(H 3 PO 4 ) 0.11 carbonized at 700 °C exhibits H 2 permeability of 200 Barrer and H 2 /CO 2 selectivity of 60 at 200 °C, and H 2 permeability of 240 Barrer and H 2 /CO 2 selectivity of 54 at 225 °C, which meets the targeted properties and surpasses Robeson’s upper bound. During the BP2, we focused on the conversion of the advanced CMS materials to stable HFMs. Membranes with H 2 permeance of 1,090 GPU (1 GPU = 10 -6 cm 3 (STP) cm -2 s -2 cmHg -1 ) and H 2 /CO 2 selectivity of 57 at 300 °C were successfully fabricated. The effects of temperature, gas compositions, pressure, and time on the separation properties were systematically investigated. Pencil modules were continuously evaluated for 219 h (dry pure gas) and 669 h (dry simulated syngas) and showed initial decline in permeance and increased H 2 /CO 2 selectivity over time, ultimately achieving a steady state stable value, indicating that the ageing phenomena in the nanoporous structures of the membranes during the test. Membrane reactors were fabricated based on the CMS membranes and evaluated for water-gas shift (WGS) reaction. The use of membranes slightly improves the conversion of the CO. However, parametric tests of the membrane reactors at various temperatures and flow rates need to be conducted, as well as the membranes with improved separation performance. We performed a sensitivity analysis on the impact of H 2 /CO 2 selectivity on the COE based on a hybrid process of a membrane unit and cryogenic unit developed by Membrane Technology and Research, Inc. (MTR). Three H 2 /CO 2 selectivity (40, 60, and 15) cases were developed and compared with the baseline capture process (Case B5B) provided by the DOE report. Increasing the membrane H 2 /CO 2 selectivity reduces COE, but the rate of the decrease of COE also diminishes. The COE values for H 2 /CO 2 selectivities of 40 and 60 were nearly the same. As the H 2 /CO 2 selectivity increases, the inert recycling decreases, leading to smaller equipment, less auxiliary power requirements, and less heating, cooling, and refrigeration duty. The refrigeration system used to liquefy the CO 2 is the most expensive piece of equipment and consumes the most electricity within the CO 2 capture process. Increasing the CO 2 concentration in the recycle stream would improve the economics of the process by reducing the refrigeration duty requirement of the unit and also allow for higher liquefaction temperatures. The high H 2 -selective membrane developed by our team may be applicable in other separation processes where lower pressure H 2 retains value. Typically, hydrogen retains its pressure when it is separated from syngas components. Residual components may be used as low-quality fuel and then vented to the atmosphere. Applications might include control of H 2 /CO ratios or mitigation of the water gas shift reaction by CO 2 recycling to the feed of a gasifier or steam methane reformer. To summarize, we have developed industrial HFMs with the best H 2 /CO 2 separation performance reported in the literature. The membranes demonstrate stability with simulated syngas and show great potential for membrane reactors for WGS reactions, lowering the cost of blue H 2 production.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Toward a Photomagnetic Mechanism for f-element separations (Final Technical Report)

The intent behind this proposal was to evaluate magnetic field effects of rare-earth ions on radical pairs. Rare-earth ions are notoriously challenging to separate based on similar thermodynamic characteristics (e.g. solubility) or ion radius, whereas magnetism varies starkly from rare-earth to rare-earth, even when ions are immediately adjacent on the periodic table. Magnetism could be a useful property then for separations, but a mechanism that is effective and selective for magnetic characteristics must be produced. A reactive mechanism for separations could likewise be interesting for selective separations, if a magnetic handle for such a separation could be defined. This proposal sought to understand a specific reactive, magnetic handle for a reactive separations scheme by creating proof of concept model complexes that place rare earths in proximity to photochemically active functional groups.

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

The Effect of Acceleration on the Separation Force in Constrained-Surface Stereolithography

Constrained-surface-based stereolithography has recently attracted much attention from both academic and industrial communities. Despite numerous experimental, numerical and theoretical efforts, the fundamental need to reduce the separation force between the newly cured part and constrained surface has not yet been completely solved. In this paper, we develop a fluid dynamics approach, proposed in our previous work, to theoretically model the separation force in 3D printing of a cylindrical part for flat and patterned windows. We demonstrate the possibility of separation force reduction with an accelerated movement of the printing platform. In particular, we investigate behaviors of transient parameter, its reduction rate, and separation force reduction with respect to elevation speed and time. The proposed approach involves deceleration and acceleration stages and allows to achieve the force reduction for the entire printing process. Finally, we provide implicit analytical solutions for time moments when switching between the stages can be done without noticeable increase of separation force and explicit expression for separation force in case of patterned window.

Gritsenko, Dmitry (ORCID:0000000248181512)↗
DOE OSTI2016

TILT ANGLE AND FOOTPOINT SEPARATION OF SMALL AND LARGE BIPOLAR SUNSPOT REGIONS OBSERVED WITH HMI

We investigate bipolar sunspot regions and how tilt angle and footpoint separation vary during emergence and decay. The Helioseismic and Magnetic Imager on board the Solar Dynamic Observatory collects data at a higher cadence than historical records and allows for a detailed analysis of regions over their lifetimes. We sample the umbral tilt angle, footpoint separation, and umbral area of 235 bipolar sunspot regions in Helioseismic and Magnetic Imager—Debrecen Data with an hourly cadence. We use the time when the umbral area peaks as time zero to distinguish between the emergence and decay periods of each region and we limit our analysis of tilt and separation behavior over time to within ±96 hr of time zero. Tilt angle evolution is distinctly different for regions with small (≈30 MSH), midsize (≈50 MSH), and large (≈110 MSH) maximum umbral areas, with 45 and 90 MSH being useful divisions for separating the groups. At the peak umbral area, we determine median tilt angles for small (7.°6), midsize (5.°9), and large (9.°3) regions. Within ±48 hr of the time of peak umbral area, large regions steadily increase in tilt angle, midsize regions are nearly constant, and small regions show evidence of negative tilt during emergence. A period of growth in footpoint separation occurs over a 72-hr period for all of the regions from roughly 40 to 70 Mm. The smallest bipoles (<9 MSH) are outliers in that they do not obey Joy's law and have a much smaller footpoint separation. We confirm the Muñoz-Jaramillo et al. results that the sunspots appear to be two distinct populations.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2012

Phase-separated, epitaxial composite cap layers for electronic device applications and method of making the same

An electronic component that includes a substrate and a phase-separated layer supported on the substrate and a method of forming the same are disclosed. The phase-separated layer includes a first phase comprising lanthanum manganate (LMO) and a second phase selected from a metal oxide (MO), metal nitride (MN), a metal (Me), and combinations thereof. The phase-separated material can be an epitaxial layer and an upper surface of the phase-separated layer can include interfaces between the first phase and the second phase. The phase-separated layer can be supported on a buffer layer comprising a composition selected from the group consisting of IBAD MgO, LMO/IBAD-MgO, homoepi-IBAD MgO and LMO/homoepi-MgO. The electronic component can also include an electronically active layer supported on the phase-separated layer. The electronically active layer can be a superconducting material, a ferroelectric material, a multiferroic material, a magnetic material, a photovoltaic material, an electrical storage material, and a semiconductor material.

36 MATERIALS SCIENCE↗
DOE OSTI2013

An advanced hybrid reprocessing system based on UF{sub 6} volatilization and chromatographic separation

To recover U, Pu, MA (Np, Am, Cm) and some specific fission products FPs (Cs, Sr, Tc, etc.) from various spent nuclear fuels (LWR/FBR: Oxide, Metal Fuels), we are studying an advanced hybrid reprocessing system based on UF6 volatilization (Pyro) and chromatographic separation (Aqueous). Spent fuels are de-cladded by means of thermal and mechanical methods and then applied to the fluorination/volatilization process, which selectively recovers the most amount of U. Then, the remained fuel components are converted to oxides and dissolved by HNO{sub 3} solution. Compared to U, since Pu, MA and FPs are significantly less abundant in spent fuels, the scale of the aqueous separation process could become reasonably small and result in less waste. For the chromatographic separation processes, we have prepared different types of porous silica-based organic/inorganic adsorbents with fast diffusion kinetics, improved chemical stability and low pressure drop in a packed column. So they are advantageously applicable to efficient separation of the actinides and FP elements from the fuel dissolved solution. In this work, adsorption and separation behavior of representative actinides and FP elements was studied. Small scale separation tests using simulated and genuine fuel dissolved solutions were carried out to verify the feasibility of the proposed process. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Facile Separation of Sr-90, Fe-55, Nb-94, Ni-59,63 with Large Amount of Ca by Controlled pH Precipitation - 17190

it is important to manage low-and intermediate-level radioactive wastes from nuclear power plants due to a permanent disposal. According to the Nuclear Safety and Security Commission (NSSC), among all the regulatory radionuclides, a few radionuclides from the fission products and corrosion products such as Sr-90, Fe-55, Nb-94, Ni-59,63 which emit low-energy x-ray and beta radiation. Thus, it is necessary to separate beta-emitting nuclides individually. For that reason, KAERI has established analytical procedures which can separate Sr-90, Fe-55, Nb-94, Ni-59,63 from radioactive waste samples. However, when radioactive wastes contain large amount of Ca (above 300 mg), it is not easy to recover the target radionuclides because high concentration of Ca has a strong influence on the effective analyses. In order to combat this problem, there was an attempt to make the precipitate as CaF{sub 2} by using hydrofluoric acid. However, this way had a limitation; Fe-55, Nb-94 were precipitated as fluoride compounds as well as Ca. In this study, we have focused on developing a separation procedure stage by stage in the radioactive wastes with Sr-90, Fe-55, Nb-94, Ni-59,63 and large amount of Ca (1500 mg). The detailed steps are described below; (1) Separation of Fe-55, Nb-94, Ni-59,63 as metal hydroxide precipitates: low solubility product constant (Ksp) between pH 6 and pH 10. (2) Selective elimination of Ca-oxalate complex under strong acidic conditions. Consequently, all the metal sources were sequentially separated and quantitatively recovered by inductively coupled plasma atomic emission spectrometric (ICP-AES) analysis, the recovery is as follows; Sr-90 (3 mg): 89.47±5.48%, Fe-55 (20 mg): 99.80±3.19%, Nb-94 (20 mg): 97.45±2.42%, Ni-59,63 (2 mg): 83.59±15.31%, Ca (1500 mg): 85.32±6.38%, respectively. This methodology will help us separation of radioactive wastes efficiently if apply properly. (authors)

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2019

Revisit of Phase Separation of Borosilicate Glass for Vitrification of High Level Radioactive Waste - 19166

Phase separation of glasses for vitrification of high level radioactive waste has been experimentally studied to know uncertainty of the phase separation conditions; temperature and glass compositions as well as to propose possibility of recycling of heavy metals on a longer time scale. Our current results at 700 and 750 deg. C for ternary borosilicate glass system showed that the phase separation region at 700 deg. C spreads along with a direction of increasing Na{sub 2}O composition when compared with the data in literature. On the other hand, at the glass composition employed in the reprocessing plant in Japan, no segregation was observed. Concerning the application of phase separation phenomena, we had previously reported recovery of almost all elements from the vitrified borosilicate glass containing simulated fission products through phase separation of the borosilicate glass and this suggests that we could propose that after vitrification of high-level radioactive waste heavy metals may be retrieved as energy or materials resources when they are required to utilize on a longer time scale. From this standpoint, phase separation of lead borosilicate glass was also studied to seek economical and versatile recycling. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

The Flow Visualization for the Separation of Air-water Bubbly Two-phase Flow Through a Vertical T-junction

T-junction is a typical structure in many industrial systems such as power plants, chemical process, and hydrocarbon production industries. The separation of two-phase flow passing through T-junction is a common flow phenomenon. There are lots of investigations regarding two-phase flow separation in branching tees and wyes tees. The characteristic of the two-phase flow between the two outlets are always non-uniform, and this kind of fluid status may contribute to the unpredictable damage of downstream facilities. For the nuclear power plants, severe accidents analysis is important especially for Light-Water Reactors (LWR) when Loss of Coolant Accident (LOCA) occurs. The small break of the pipe may cause the coolant become two-phase flow due to the pressure drop. Under certain conditions, the behavior of T-junction is similar to a gas-liquid separator, as a result of the gas enters the side arm and the liquid flows straight along the run arm. The partial separation of gas-liquid mixtures can reduce the load on the main separator, probably leading to smaller units. The study aims to establish complete visual observations for the benchmark of Computational Fluid Dynamics (CFD) model. As a consequence, a vertical T-junction (D = 26 mm) experimental loop was set up for the purpose of elaborating the complex two-phase fluid phenomena. In this experiment, variables were manipulated under highly controlled conditions and a photographic method was proposed to analyze the images of phase separation. Furthermore, the images obtained by camera have been discussed to receive valuable information about the two phase flow behavior around the T-junction.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Simulation studies for beam commissioning at FRIB Advanced Rare Isotope Separator

The Facility for Rare Isotope Beams (FRIB) includes a powerful superconducting driver accelerator and an Advanced Rare Isotope Separator (ARIS). The ARIS collects and purifies the rare isotope fragments of interest for experiments in nuclear physics, nuclear astrophysics, fundamental symmetries, etc. ARIS consists of a vertical pre-separator and downstream horizontal separator section (C-Bend). Each section can provide a high-resolution separation alternatively. The resolution reduction due to the emittance induced by momentum compression can be avoided by isotope separation in different dispersive planes. Beam commissioning of ARIS for the first experiments was completed and demonstrated particle identification of fragments. The beam tuning in ARIS largely relies on numerical simulations since the limited space for diagnostics. Here, we report the result of the beam trajectory correction, transverse matching, and beam-based misalignment studies at ARIS.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2023

Adaptive Pore Opening to Form Tailored Adsorption Sites in a Cooperatively Flexible Framework Enables Record Inverse Propane/Propylene Separation

A proposed low-energy alternative to the separation of alkanes from alkenes by energy-intensive cryogenic distillation is separation by porous adsorbents. Unfortunately, most adsorbents preferentially take up the desired, high-value major component alkene, requiring frequent regeneration. Adsorbents with inverse selectivity for the minor component alkane would enable the direct production of purified, reagent-grade alkene, greatly reducing global energy consumption. However, such materials are exceedingly rare, especially for propane/propylene separation. Here, we report that through adaptive and spontaneous pore size and shape adaptation to optimize an ensemble of weak noncovalent interactions, the structurally responsive metal-organic framework CdIF-13 (sod-Cd(benzimidazolate) 2 ) exhibits inverse selectivity for propane over propylene with record-setting separation performance under industrially relevant temperature, pressure, and mixture conditions. Powder synchrotron X-ray diffraction measurements combined with first-principles calculations yield atomic-scale insight and reveal the induced fit mechanism of adsorbate-specific pore adaptation and ensemble interactions between ligands and adsorbates. Dynamic column breakthrough measurements confirm that CdIF-13 displays selectivity under mixed-component conditions of varying ratios, with a record measured selectivity factor of α ≈ 3 at 95:5 propylene:propane at 298 K and 1 bar. When sequenced with a low-cost rigid adsorbent, we demonstrated the direct purification of propylene under ambient conditions. In conclusion, this combined atomic-level structural characterization and performance testing firmly establishes how cooperatively flexible materials can be capable of unprecedented separation factors.

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

Benchmarking Hydrogen Isotope Separation Efficiency of Pd/k–Packed TCAP Columns

By leveraging the large isotope effect in the palladium hydrogen isotope system, the Thermal Cycling Absorption Process (TCAP) provides an efficient and advantageous means to separate protium, deuterium, and tritium. To meet increased future tritium processing demands, such as those needed for fusion power plants, current designs of the separation columns need to be adapted and optimized using the progress made in understanding hydrogen isotope science. One key to this optimization lies in understanding the baseline performance for currently employed separation packing materials. Pd/k and molecular sieves, as commonly used for the separation of hydrogen isotopes, are herein evaluated to establish a baseline for their separation efficiency. Van Deemter plots are formulated, and the influence of each parameter is evaluated to determine areas for improvement.

Thermal Cycling Absorption Process (TCAP)↗
DOE OSTI2014

Development of the Actinide-Lanthanide Separation (ALSEP) Process

Separating the minor actinide elements (Am and Cm) from acidic high-level raffinates arising from the reprocessing of irradiated nuclear fuel is an important step in closing the nuclear fuel cycle. Most proposed approaches to this problem involve two solvent extraction steps: 1) co-extraction of the trivalent lanthanides and actinides, followed by 2) separation of the actinides from the lanthanides. The objective of our work is to develop a single solvent-extraction process for isolating the minor actinide elements. We report here a solvent containing N,N,N',N'-tetra(2 ethylhexyl)diglycolamide (T2EHDGA) combined with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) that can be used to separate the minor actinides in a single solvent-extraction process. T2EHDGA serves to co-extract the trivalent actinide and lanthanide ions from nitric acid solution. Switching the aqueous phase chemistry to a citrate buffered solution of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid at pH 2.5 to 4 results in selective transfer of the actinides to the aqueous phase, thus affecting separation of the actinides from the lanthanides. Separation factors between the lanthanides and actinides are approximately 20 in the pH range of 3 to 4, and the distribution ratios are not highly dependent on the pH in this system.

actinide separation↗
DOE OSTI2024

Tailorable Multi–Modular Pore–Space–Partitioned Vanadium Metal–Organic Frameworks for Gas Separation

Currently, few porous vanadium metal-organic frameworks (V-MOFs) are known and even fewer are obtainable as single crystals, resulting in limited information on their structures and properties. Here this work demonstrates remarkable promise of V-MOFs by presenting an extensible family of V-MOFs with tailorable pore geometry and properties. The synthesis leverages inter-modular synergy on a tri-modular pore-partitioned platform. New V-MOFs show a broad range of structural features and sorption properties suitable for gas storage and separation applications for C 2 H 2 /CO 2 , C 2 H 6 /C 2 H 4 , and C 3 H 8 /C 3 H 6 . The c/a ratio of the hexagonal cell, a measure of pore shape, is tunable from 0.612 to 1.258. Other tunable properties include pore size from 5.0 to 10.9 Å and surface area from 820 to 2964 m 2 g –1 . With C 2 H 2 /CO 2 selectivity from 3.3 to 11 and high uptake capacity for C 2 H 2 from 65.2 to 182 cm 3 g –1 (298K, 1 bar), an efficient separation is confirmed by breakthrough experiments. The near-record high uptake for C 2 H 6 (166.8 cm 3 g –1 ) contributes to the promise for C 2 H 6 -selective separation of C 2 H 6 /C 2 H 4 . The multi-module pore expansion enables transition from C 3 H 6 -selective to more desirable C 3 H 8 -selective separation with extraordinarily high C 3 H 8 uptake (254.9 cm 3 g –1 ) and high separation potential (1.25 mmol g –1 ) for C 3 H 8 /C 3 H 6 (50:50 v/v) mixture.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Integrated Bare Narrow Capillary-Hydrodynamic Chromatographic System for Free-Solution DNA Separation at the Single-Molecule Level

We have recently introduced a new technique, Bare Narrow Capillary Hydrodynamic Chromatography (BaNC–HDC), to resolve DNA without sieving matrices. In this technique, the separation capillaries had a diameter usually from a few hundred nanometers to a few micrometers. While high resolutions were obtained (especially for large DNA fragments), the sample injection and DNA elution were tedious, and the separation results (peak areas) were not reproducible. This was caused by the extremely low injection volumes (a few picoliters) and elution rates (<1 nanoliter per minute), which prevented us from utilizing reliable injection valves and commercial high performance liquid chromatographic pumps. In this work, we incorporate a microfabricated chip injector, and a high-pressure electroosmotic pump (EOP) to address these issues. The chip injector allows us to reliably and reproducibly inject low volumes (as low as ~1 pL) of samples into the narrow separation capillary, while the EOP provides flow rates and pressures perfectly suited for BaNC–HDC separations. Using the above system, we resolve kilo base-pair DNA fragments rapidly (in a few min) with high resolutions, and the limit of detection for double stranded DNA reaches a few molecules. The experimental parameters affecting resolutions are also discussed. Incorporation of a chip injection scheme makes automating BaNC–HDC separations readily achievable.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Pore Aperture Control Toward Size‐Exclusion‐Based Hydrocarbon Separations

Metal–organic frameworks (MOFs) have been proposed as a promising material for non-thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well-defined pore apertures/channels with sub-Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi-component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗