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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 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Metal–Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation

The removal of carbon dioxide (CO 2 ) from acetylene (C 2 H 2 ) is a critical industrial process for manufacturing high purity C 2 H 2 . However, it remains challenging to address the trade-off between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of hydrogen-bonding nanotrap on the pore surface to promote the separation of C 2 H 2 /CO 2 mixtures, in three isostructural metal-organic frameworks (MOFs, named as MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates ultra-high C 2 H 2 storage capacity (191 cm 3 g –1 , or 213 cm 3 cm –3 ) but much less CO 2 uptake (90 cm 3 g –1 ) under ambient conditions. The C 2 H 2 adsorption amount of MIL-160 is remarkably higher than the other two isostructural MOFs (86 cm 3 g –1 and 119 cm 3 g –1 for CAU-10H and CAU-23 respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C 2 H 2 /CO 2 separation in terms of the separation potential (Δq break = 5.02 mol/kg) and C 2 H 2 productivity (6.8 mol/kg). In addition, in-situ FT-IR experiments combined with computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interactions between the nanotrap and C 2 H 2 is the key factor for achieving extraordinary acetylene storage capacity and superior C 2 H 2 /CO 2 selectivity. Furthermore, this work provides a novel and powerful approach to address the trade-off of this extremely challenging gas separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Metal–Organic Framework Containing Planar Metal-Binding Sites: Efficiently and Cost-Effectively Enhancing the Kinetic Separation of C 2 H 2 /C 2 H 4

One of the emerging problems plaguing the chemical industry today is the efficient and cost-effective separation of C 2 hydrocarbons. In order to help address this problem, we report a new material, NbU-1, constructed by extremely cheap starting materials. The special structural characteristics of NbU-1 such as the planar, mixed-valence copper clusters and Lewis-basic adsorption channels enforce interactions with acetylene molecules that lead to the highest kinetic separation efficiency for C 2 H 2 /C 2 H 4 . Via DFT-D calculations, it is indicated that C 2 H 2 molecules are adsorbed onto the two adjacent Cu(I) centers, but not the usual single open metal sites of Cu centers. Here, the reported results not only provide information for a deep investigation into the separation mechanism but also offer an alternative strategy for preparing cost-effective materials that can perform highly efficient separations of light hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Phase separation during bulk polymerization of methyl methacrylate

We report on the phase separation of methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) during bulk free-radical polymerization. The phase separation is induced when the reaction is initiated at room temperature by the redox reaction of benzoyl peroxide in the presence of an amine. During the reaction, the ratio of MMA and PMMA changes continuously. Separation into MMA-rich and PMMA-rich phases coincides with the onset of the Trommsdorff effect. At room temperature, the interface between the two phases remains, even after drying the remaining monomer. When the sample is annealed above the glass transition temperature Tg, the interface disappears. Due to the frozen dynamics of the polymer chains, subsequent cooling below Tg does not result in further phase separation. This result provides evidence for the existence of rich, thermodynamically stable states, which are typically suppressed due to the frozen dynamics of polymers at temperatures below the Tg, after thermal processing above the Tg.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

Mixed halide hybrid perovskites, CH 3 NH 3 Pb(I 1-x Brx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Excitonic structure and charge separation in the heliobacterial reaction center probed by multispectral multidimensional spectroscopy

Photochemical reaction centers are the engines that drive photosynthesis. The reaction center from heliobacteria (HbRC) has been proposed to most closely resemble the common ancestor of photosynthetic reaction centers, motivating a detailed understanding of its structure-function relationship. The recent elucidation of the HbRC crystal structure motivates advanced spectroscopic studies of its excitonic structure and charge separation mechanism. We perform multispectral two-dimensional electronic spectroscopy of the HbRC and corresponding numerical simulations, resolving the electronic structure and testing and refining recent excitonic models. Through extensive examination of the kinetic data by lifetime density analysis and global target analysis, we reveal that charge separation proceeds via a single pathway in which the distinct A 0 chlorophyll a pigment is the primary electron acceptor. In addition, we find strong delocalization of the charge separation intermediate. Our findings have general implications for the understanding of photosynthetic charge separation mechanisms, and how they might be tuned to achieve different functional goals.

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

Enhanced rare-earth separation with a metal-sensitive lanmodulin dimer

Technologically critical rare-earth elements are notoriously difficult to separate, owing to their subtle differences in ionic radius and coordination number. The natural lanthanide-binding protein lanmodulin (LanM) is a sustainable alternative to conventional solvent-extraction-based separation. Here we characterize a new LanM, from Hansschlegelia quercus (Hans-LanM), with an oligomeric state sensitive to rare-earth ionic radius, the lanthanum(III)-induced dimer being >100-fold tighter than the dysprosium(III)-induced dimer. X-ray crystal structures illustrate how picometre-scale differences in radius between lanthanum(III) and dysprosium(III) are propagated to Hans-LanM’s quaternary structure through a carboxylate shift that rearranges a second-sphere hydrogen-bonding network. Comparison to the prototypal LanM from Methylorubrum extorquens reveals distinct metal coordination strategies, rationalizing Hans-LanM’s greater selectivity within the rare-earth elements. Finally, structure-guided mutagenesis of a key residue at the Hans-LanM dimer interface modulates dimerization in solution and enables single-stage, column-based separation of a neodymium(III)/dysprosium(III) mixture to >98% individual element purities. This work showcases the natural diversity of selective lanthanide recognition motifs, and it reveals rare-earth-sensitive dimerization as a biological principle by which to tune the performance of biomolecule-based separation processes.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Theoretical Insights into Covalency Driven f Element Separations

The lanthanide series, Am, and Cm are predominantly found in the trivalent oxidation state in aqueous solutions making their separation very difficult to achieve. To date, one of the mostly promising separation processes for transplutonium elements from the lanthanides is the TALSPEAK process. Though the mechanism of the TALSPEAK process is not fully understood, it has been demonstrated to provide excellent separation factors between the lanthanides and the trivalent lanthanides. Through Density Function Theory (DFT) calculations of di 2-ethylenetriamine-N,N,N',N”,N”-pentaacetic acid (DTPA), we set out to understand the structures and stabilities of the aqueous phase complexes [MIII(DTPA)-H2O]2- (M = Nd, Am) as well as the changes in Gibbs free energy for complexation in the gas phase and aqueous solution. Mulliken population analysis, Bader’s Atoms-in-Molecules (AIM) approach, and Natural Bond Orbital (NBO) analysis were then used to analyze the bonding in both molecules. The results discussed below suggest that the preference of the DTPA5- ligand for Am over Nd is mainly due to electrostatic and covalent interactions from the oxygen atoms with the nitrogen chelates provide an additional, yet small, covalent interaction. These results question the exclusive use of hard and soft acids and bases (HSAB) concepts for the design of extracting reagents and suggest that hard-soft interactions play more of a role in the separations process than previously thought.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

The direct observation of charge separation dynamics in CdSe quantum dots/cobaloxime hybrids

In this work, we investigated photoinduced charge separation dynamics in a CdSe quantum dot/cobaloxime molecular catalyst hybrid using the combination of transient optical (OTA) and X-ray absorption (XTA) spectroscopy. We show that ultrafast charge separation occurs through electron transfer (ET) from CdSe QDs to cobaloxime. In addition to the enhanced 1S exciton bleach recovery in CdSe QDs due to the presence of cobaloxime, the direct evidence for ET process, i.e. the formation of the transient charge separated state, is captured by XTA. These results not only demonstrate the capability of XTA to capture the transient species during the photoinduced reactions in hybrid nanostructures but also enhance our understanding of charge separation dynamics in semiconductor nanocrystal/molecular catalyst hybrid

Huang, J.↗
DOE OSTI2016

The effect of Mo doping on the charge separation dynamics and photocurrent performance of BiVO 4 photoanodes

Doping with electron-rich elements in BiVO 4 photoanodes has been demonstrated as a desirable approach for improving their carrier mobility and charge separation efficiency. However, the effect of doping and dopant concentration on the carrier dynamics and photoelectrochemical performance remains unclear. In this work, we examined the effects of Mo doping on the charge separation dynamics and photocurrent performance in BiVO 4 photoanodes. We show that the photocurrent of BiVO 4 photoanodes increases with increasing concentration of the Mo dopant, which can be attributed to both the improved carrier mobility resulting from increased electron density and charge separation efficiency due to the diminishing of trap states upon Mo doping. The effect of doping on the electronic structure, carrier dynamics and photocurrent performance of BiVO 4 photoanodes resulting from W and Mo dopants was also compared and discussed in this study. The knowledge gained from this work will provide important insights into the optimization of the carrier mobility and charge separation efficiency of BiVO 4 photoanodes by controlling the dopants and their concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Synthesis and radiometric evaluation of diglycolamide functionalized mesoporous silica for the chromatographic separation of actinides Th, Pa and U

The separation of Th, Pa, and U is of critical importance in many applications including nuclear power, nuclear waste, environmental and geochemistry, nuclear forensics and nuclear medicine. Diglycolamide (DGA)-based resins have shown the ability to separate many elements, yet, these resins consist of non-covalent impregnation of the DGA molecules on the resin backbone resulting in co-elution of the extraction molecule during separation cycles, therefore limiting their long-term and repeated use. Covalently binding the DGA molecules onto silica is one way to overcome this issue. Herein, measured equilibrium distribution coefficients of normal extraction chromatographic DGA resin and a covalently bound form (KIT-6-N-DGA sorbent) are reported. Several differences are observed between the two systems, the most significant being observed for uranium, which demonstrated significantly lower sorption behavior on KIT-6-N-DGA. These results indicate that U can effectively be separated from Th and Pa using KIT-6-N-DGA, a task that could not be completed with the use of normal DGA alone.

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

Phase separation and state oscillation of active inertial particles

Active matter systems are of great interest for their novel out-of-equilibrium collective behavior. Active Brownian particles (ABPs) are known to exhibit clustering and motility-induced phase separation, and there have been many studies revealing this rich behavior in the overdamped limit of Brownian motion, where inertial effects are insignificant. In this work, we simulate an Active Inertial Particle (AIP) model where we focus on the underdamped, rather than overdamped limit, to study the interplay between particle inertia and collective behavior, such as phase separation. We show that inertia reduces particle motility due to collisions and a longer time delay for particles to regain speed, thereby suppressing phase separation relative to that observed in the overdamped limit. Additionally, we observe interesting oscillatory behavior between a phase separated steady-state and a homogeneous fluid state that results from inertia-induced collective motion within active clusters due to momentum transfer. Such oscillatory behavior has been reported for ABP systems with particle shape anisotropy, where collective motion is mediated by particle shape anisotropy. Furthermore, we confirm that there is no single characteristic frequency for the oscillatory behavior. The power spectral density is a power law in the high frequency domain, with an exponent close to -2.5.

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

Investigation of a bacteriochlorin-containing pentad array for panchromatic light-harvesting and charge separation

A new pentad array designed to exhibit panchromatic absorption and charge separation has been synthesized and characterized. The array is composed of a triad panchromatic absorber (a bis(perylene-monoimide)-porphyrin) to which are appended an electron acceptor (perylene-diimide) and an electron donor/hole acceptor (bacteriochlorin) in a crossbar arrangement. The motivation for incorporation of the bacteriochlorin versus a free-base or zinc chlorin utilized in prior constructs was to facilitate hole transfer to this terminal unit and thereby achieve a higher yield of charge separation across the array. The intense S 0 → S 1 (Q y ) band of the bacteriochlorin also enhances absorption in the near-infrared spectral region. Due to synthetic constraints, a phenylethyne linker was used to join the bacteriochlorin to the core porphyrin of the panchromatic triad rather than the diphenylethyne linker employed for the prior chlorin-containing pentads. Static and time-resolved photophysical studies reveal enhanced excited-state quenching for the pentad in benzonitrile and dimethyl sulfoxide compared to the prior chlorin-containing analogues. Success was only partial, however, as a long-lived charge separated state was not observed despite the improved energetics for the final ground-state hole/electron-shift reaction. The apparent reason is more facile competing charge-recombination due to the shorter bacteriochlorin – porphyrin linker that increases electronic coupling for this process. Furthermore, the studies highlight design criteria for balancing panchromatic absorption and long-lived charge separation in molecular architectures for solar-energy conversion.

14 SOLAR ENERGY↗
DOE OSTI2022

Metal–organic frameworks as O 2 -selective adsorbents for air separations

Oxygen is a critical gas in numerous industries and is produced globally on a gigatonne scale, primarily through energy-intensive cryogenic distillation of air. The realization of large-scale adsorption-based air separations could enable a significant reduction in associated worldwide energy consumption and would constitute an important component of broader efforts to combat climate change. Certain small-scale air separations are carried out using N 2 -selective adsorbents, although the low capacities, poor selectivities, and high regeneration energies associated with these materials limit the extent of their usage. In contrast, the realization of O 2 -selective adsorbents may facilitate more widespread adoption of adsorptive air separations, which could enable the decentralization of O 2 production and utilization and advance new uses for O 2 . Here, we present a detailed evaluation of the potential of metal–organic frameworks (MOFs) to serve as O 2 -selective adsorbents for air separations. Drawing insights from biological and molecular systems that selectively bind O 2 , we survey the field of O 2 -selective MOFs, highlighting progress and identifying promising areas for future exploration. As a guide for further research, the importance of moving beyond the traditional evaluation of O 2 adsorption enthalpy, ΔH, is emphasized, and the free energy of O 2 adsorption, ΔG, is discussed as the key metric for understanding and predicting MOF performance under practical conditions. Based on a proof-of-concept assessment of O 2 binding carried out for eight different MOFs using experimentally derived capacities and thermodynamic parameters, we identify two existing materials and one proposed framework with nearly optimal ΔG values for operation under user-defined conditions. While enhancements are still needed in other material properties, the insights from the assessments herein serve as a guide for future materials design and evaluation. Computational approaches based on density functional theory with periodic boundary conditions are also discussed as complementary to experimental efforts, and new predictions enable identification of additional promising MOF systems for investigation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Facets control charge separation during photoelectrochemical water oxidation with strontium titanate (SrTiO 3 ) single crystals

The photocatalytic overall water splitting reaction provides a pathway to hydrogen fuel from sunlight. Photocatalysts must achieve the reaction without the application of an external bias, which requires an effective charge separation mechanism. Photolabeling studies and electrostatic simulations for the well-known CoOOH/Al:SrTiO 3 /Rh/Cr 2 O 3 photocatalyst suggest that charge separation is driven by work function differences at the (100) and (110) facets of SrTiO 3 , which are electron and hole selective, respectively. Here we use hydrogen annealed SrTiO 3–x single crystals to obtain the first quantitative assessment of the charge separation ability of the (100), or (110), or (111) facets during oxygen evolution. Under UV illumination (60 mW cm –2 ), the crystals exhibit variable water oxidation photocurrents (0.34, 0.82, 1.36 mA cm –2 at 1.23 V versus RHE) and photovoltage values of 1.40, 1.52 and 1.52 V for (100), (110), and (111) SrTiO 3–x , respectively. A surface photovoltage increase in that same order (0.31 V < 0.57 V < 0.67 V) is confirmed independently with vibrating Kelvin probe surface photovoltage spectroscopy (VKP-SPV) under 375 nm (1.91 mW cm –2 ) illumination. Mott Schottky measurements in aqueous K 3/4 [Fe(CN) 6 ] reveal facet-dependent flatband positions of –0.58, –0.71, and –0.74 V RHE for the (100), (110), and (111) crystals respectively. This confirms that the photoelectrochemical water oxidation performance of SrTiO 3–x crystals is controlled by the work function of each facet, which determines the electron transfer barrier height of the respective solid–liquid junctions. After correcting for differences in electron donor concentrations, barriers are found to increase in the order (100) < (111) < (110) and differ by as much as 0.16 eV, similar to an earlier prediction. Altogehter, these results explain the charge separation mechanism in SrTiO 3 photocatalysts and highlight the need for faceted semiconductor crystals as light absorbers in particle-based photocatalysts.

08 HYDROGEN↗
DOE OSTI2014

Advances and problems in plasma-optical mass-separation

This paper presents a short review of plasma-optical mass-separation and defines the fields for its possible application. During theoretical studies, numerical simulations, and experiments, the effect of the azimuthator finite size and of the vacuum conditions on the mass separator characteristics was revealed, as well as the quality of different-mass ion separation. The problems, solving which may lead to a successful end of the mass-separation plasma-optical technique implementation, were specified.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Continuous flow system for controlling phases separation near λ transition

As demands on 3He are increasing and conventional 3He production through tritium decay is decreasing, alternative 3He production methods are becoming economically viable. One such possibility is to use entropy filters for extraction of the 3He isotope from natural gas. According to the phase diagram of the 3He, its solidification is impossible by only lowering of the temperature. Hence during the cooling process at stable pressure we can reach λ-point and pass to the special phase - He II. The total density of HeII is a sum of the two phases: normal the superfluid ones. It is possible to separate these two phases with an entropy filter - the barrier for the classically-behaving normal phase. This barrier can also be used to separate the two main isotopes of He: 4He and 3He, because at temperatures close to the 4He-λ-point the 3He isotope is part of the normal phase. The paper presents continuous flow schemes of different separation methods of 3He from helium commodity coming from natural gas cryogenic processing. An overall thermodynamic efficiency of the 3He/4He separation process is presented. A simplified model of continuous flow HeI -HeII recuperative heat exchanger is given. Ceramic and carbon porous plugs have been tested in entropy filter applications.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Nanoporous separators for supercapacitor using activated carbon monolith electrode from oil palm empty fruit bunches

Activated porous carbon electrode prepared from fibres of oil palm empty fruit bunches was used for preparing the carbon based supercapacitor cells. The symmetrical supercapacitor cells were fabricated using carbon electrodes, stainless steel current collector, H{sub 2}SO{sub 4} electrolyte, and three types of nanoporous separators. Cells A, B and C were fabricated using polypropylene, eggshell membrane, and filter paper, respectively. Electrochemical characterizations data from Electrochemical Impedance Spectroscopy, Cyclic Voltammetry, and Galvanic Charge Discharge techniques showed that specific capacitance, specific power and specific energy for cell A were 122 F g{sup −1}, 177 W kg{sup −1}, 3.42 Wh kg{sup −1}, cell B; 125 F g{sup −1}, 179 W kg{sup −1}, and 3.64 Wh kg{sup −1}, and cell C; 180 F g{sup −1}, 178 W kg{sup −1}, 4.27 Wh kg{sup −1}. All the micrographs from Field Emission Scanning Electron Microscope showed that the different in nanoporous structure of the separators lead to a significant different in influencing the values of specific capacitance, power and energy of supercapacitors, which is associated with the mobility of ion into the pore network. These results indicated that the filter paper was superior than the eggshell membrane and polypropylene nanoporous separators. However, we found that in terms of acidic resistance, polypropylene was the best nanoporous separator for acidic medium.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Helical path separation for guided wave tomography

The pipe wall loss caused by corrosion can be quantified across an area by transmitting guided Lamb waves through the region and measuring the resulting signals. Typically the dispersive relationship for these waves, resulting in the wave velocity being a function of thickness, is exploited which enables the wall thickness to be determined from a velocity reconstruction. The accuracy and quality of this reconstruction is commonly limited by the angle of view available from the transducer arrays. These arrays are often attached as a pair of ring arrays either side of the inspected region, and due to the cyclic nature of the pipe, waves are able to travel in an inifinite number of helical paths between any two transducers. The first arrivals can be separated relatively easily by time gating, but by using just these components the angle of view is strongly restricted. To improve the viewing angle, it is necessary to separate the wavepackets. This paper provides an outline of a separation approach: initially the waves are backpropagated to their source to align the different signals, then a filtering technique is applied to select the desired components. The technique is applied to experimental data and demonstrated to robustly separate the signals.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗