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At least 163 records · Page 9

In situ reductive dissolution to remove Iodine-129 from aquifer sediments

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e., incorporated into Fe oxides), however, XANES data was inconclusive as to valence state. During groundwater leaching, aqueous and adsorbed iodine was quickly released, then additional iodine was slowly released potentially from dissolution of one or more surface phases. The Na-dithionite treatment removed greater iodine mass (2.9x) at a faster rate (1 to 4 orders of magnitude) compared to leaching with groundwater alone. Iron extractions for untreated and treated sediments showed a decrease in Fe(III)-oxides, which likely released iodine to aqueous solution. Solid phase inorganic carbon and aqueous Ca and Mg analysis further confirmed that significant calcite dissolution did not occur in these experiments meaning these phases did not release significant iodine. Although it was expected that, after treatment, 127 I concentrations would eventually be lower than untreated sediments, leaching experiments showed continued, elevated iodine concentrations for treated samples over 750 hours. Stop flow events during 1-D column leaching suggested that some iodide precipitated within the first few pore volumes. In the survey of metals during leaching, some silver was detected which could have been solubilized by the elevated pH of initial Na-dithionite injection. Then, silver (or other metals) could have subsequently precipitated with iodide during the initial stop flow event forming a slowly dissolving source. Although significantly greater iodine is removed with treatment, the long-term leaching needs to be investigated further as it may limit dithionite treatment at the field scale.

54 ENVIRONMENTAL SCIENCES↗

Noble Gas Management: SBMOF 1 vs. NUCON Carbon

Pacific Northwest National Laboratory (PNNL), in collaboration with Flibe Energy, Inc., demonstrated the fabrication of metal organic frameworks (MOFs) into engineered beads to manage off-gases released from molten salt reactors. Among the many MOF options, SBMOF 1 was selected as an ideal sorbent to manage off-gases released from a molten salt reactor because its pore size is optimal. The SBMOF 1 was synthesized and fabricated into engineered particles using three different methods, with and without polymers. All the engineered particles were exposed to Co-60 radiation (1,000 kGy) to demonstrate their radiation stability. Single column breakthrough experiments were performed at different temperatures, activation conditions, flow rates, and off-gas compositions to optimize the Xe capacity at the breakthrough point and at saturation. The Xe loading in SBMOF 1 was compared with that of standard solid sorbent (Nucon carbon) under identical conditions. Based on the single column experiments, SBMOF 1 outperforms the Nucon carbon at all the temperatures and reduces the mass (to as little as 55%) of sorbent needed to achieve the same performance as carbon. The bed volume is also reduced, down to 48% of that of Nucon carbon, when the MOF is used. These results clearly demonstrate improvement in the amount of adsorbent needed and show a reduction in bed volume compared to traditional sorbent material.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Ion solvation as a predictor of lanthanide adsorption structures and energetics in alumina nanopores

Adsorption reactions at solid-water interfaces define elemental fate and transport and enable contaminant clean-up, water purification, and chemical separations. For nanoparticles and nanopores, nanoconfinement may lead to unexpected and hard-to-predict products and energetics of adsorption, compared to analogous unconfined surfaces. Here we use X-ray absorption fine structure spectroscopy and operando flow microcalorimetry to determine nanoconfinement effects on the energetics and local coordination environment of trivalent lanthanides adsorbed on Al 2 O 3 surfaces. We show that the nanoconfinement effects on adsorption become more pronounced as the hydration free energy, ΔG hydr , of a lanthanide decreases. Neodymium (Nd 3+ ) has the least exothermic ΔG hydr (-3336 kJ·mol -1 ) and forms mostly outer-sphere complexes on unconfined Al 2 O 3 surfaces but shifts to inner-sphere complexes within the 4 nm Al 2 O 3 pores. Lutetium (Lu 3+ ) has the most exothermic ΔG hydr (-3589 kJ·mol -1 ) and forms inner-sphere adsorption complexes regardless of whether Al 2 O 3 surfaces are nanoconfined. Importantly, the energetics of adsorption is exothermic in nanopores only, and becomes endothermic with increasing surface coverage. Changes to the energetics and products of adsorption in nanopores are ion-specific, even within chemically similar trivalent lanthanide series, and can be predicted by considering the hydration energies of adsorbing ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Center for Gas Separations (CGS)

The total energy consumption in the U.S. has been rising steadily for decades, and it currently amounts to ~98,000 TBtu/yr, with approximately 30% of this total attributable to the industrial sector. Reasonable estimates indicate that 45–55% of total industry energy consumption derives from chemical separations, and for example, over 120 TBtu/yr alone is used in carrying out olefin/paraffin separations via energy-intensive cryogenic distillation. Therefore, the pursuit of new, even radically different approaches to some of the most energy-intensive industrial separations processes is an imperative scientific pursuit for reducing energy consumption toward a more sustainable future. Adsorbent and membrane-based separations can require a fraction of the energy needed for distillation methods, and as such are considered promising solutions for balancing increasing energy demand in the U.S. with the need for a massive reduction in energy consumption. Although considerable research effort has been devoted to the design of materials capable of carrying out various gas separations, usually operating through size-selective, chemisorptive, or physisorptive mechanisms, it remains a great challenge to design materials that function adequately for real-world applications. Indeed, the chemical and physical differences between molecules in gas mixtures of interest are often small, and therefore it is necessary, through the use of nanoscience and synthetic chemistry, to engineer unprecedented molecular-level control in adsorbate–adsorbent interactions. The overarching mission of the Center for Gas Separations (CGS) was to discover fundamental innovations that have the potential to dramatically reduce the energy associated with critical gas separations. In particular, the CGS developed novel synthetic routes, guided by molecular chemistry principles, as well as advanced characterization and computational methods, that have enabled the discovery of new materials and membranes tailor-made to exhibit exceptional performance for a range of gas separations processes, as required in the clean use of fossil fuels and in reducing CO 2 emissions from industry. A challenge of this magnitude required the collaboration and synergy of a large team of researchers with expertise in materials synthesis, characterization, and computations. During the 11-year project period, the CGS created a range of new materials within the family of highly-tunable, porous solids known as metal–organic frameworks (MOFs). These new frameworks demonstrate novel mechanisms for key industrial gas separations, including revolutionary new cooperative adsorption processes that enable low-energy CO 2 and CO capture, and are capable of efficiently separating olefins from paraffins, O 2 from air, and the shape-selective separation of alkane isomers. In addition, the CGS developed new strategies for incorporating these materials into composite membranes toward highly efficient and selective membrane-based separations. As a testament to the success of the CGS, two start-up companies, Mosaic Materials,4 Inc. and Flux Technology, Inc., grew out of these research efforts, and these companies are seeking to commercialize MOF and composite membranes materials for key separations in industry, including large-scale CO 2 capture and hydrocarbon separations, respectively. Another company, framergy, Inc., licensed IP resulting from CGS research toward the commercialization of adsorbents for various energy-relevant applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vanadate Retention by Iron and Manganese Oxides

Anthropogenic emissions of vanadium (V) into terrestrial and aquatic surface systems now match those of geogenic processes, and yet, the geochemistry of vanadium is poorly described in comparison to other comparable contaminants like arsenic. In oxic systems, V is present as an oxyanion with a +5 formal charge on the V center, typically described as H x VO 4 (3–x)– , but also here as V(V). Iron (Fe) and manganese (Mn) (oxy)hydroxides represent key mineral phases in the cycling of V(V) at the solid–solution interface, and yet, fundamental descriptions of these surface-processes are not available. Here, we utilize extended X-ray absorption fine structure (EXAFS) and thermodynamic calculations to compare the surface complexation of V(V) by the common Fe and Mn mineral phases ferrihydrite, hematite, goethite, birnessite, and pyrolusite at pH 7. Inner-sphere V(V) complexes were detected on all phases, with mononuclear V(V) species dominating the adsorbed species distribution. Our results demonstrate that V(V) adsorption is exergonic for a variety of surfaces with differing amounts of terminal –OH groups and metal–O bond saturations, implicating the conjunctive role of varied mineral surfaces in controlling the mobility and fate of V(V) in terrestrial and aquatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Salt Concentration on the Interfacial Solvation Structure and Early Stage of Solid–Electrolyte Interphase Formation in Ca(BH 4 ) 2 /THF for Ca Batteries

The Ca 2+ solvation structure at the electrolyte/electrode interface is of central importance to understand electroreduction stability and solid–electrolyte interphase (SEI) formation for the novel multivalent Ca battery systems. Here, using an exemplar electrolyte, the concentration-dependent solvation structure of Ca(BH 4 ) 2 -tetrahydrofuran on a gold model electrode has been investigated with various electrolyte concentrations via electrochemical quartz crystal microbalance with dissipation (EQCM-D) and X-ray photoelectron spectroscopy (XPS). For the first time, in situ EQCM-D results prove that the prevalent species adsorbed at the interface is CaBH 4 + across all concentrations. As the salt concentration increases, the number of BH 4 – anions associated with Ca 2+ increases, and much larger solvated complexes such as CaBH 4 + ·4THF or Ca(BH 4 ) 3 – ·4THF form at the interface at high concentrations prior to Ca plating. Different interfacial chemistries lead to the formation of SEIs with different components demonstrated by XPS. High electrolyte concentrations reduce the solvent decomposition and promote the formation of thick, uniform, and inorganic-rich (i.e., CaO) SEI layers, which contribute to improved Ca plating efficiency and current density in electrochemical measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dissolution and initial hydration behavior of tricalcium aluminate in low activity sulfate solutions

Influences of alkali or alkaline earth sulfates on the hydration of cubic tricalcium aluminate (C 3 A) were evaluated by in situ dissolution rate measurements, by ex situ near-surface composition measurements with secondary ion mass spectrometry, and by in situ synchrotron X-ray diffraction to monitor precipitation of hydration products. Both slight reductions in dissolution rate and cation-specific interactions with the solid were observed. The near-surface Ca/Al ratio is significantly lower after some dissolution and the electrolyte cations are incorporated within the surface with different affinities (Mg 2+ > K + > Na + ). An interfacial dissolution-reprecipitation mechanism may explain the observations as well as, or better than, a simple cation exchange. The sulfate concentration in solution affects the rates of both C 3 A dissolution and precipitation of hydration products. Aditionally, sulfate ions likely adsorb at the hydrous Al-rich surface layer, thereby reducing the dissolution rate of aluminates and delaying the precipitation of aluminate hydration products.

36 MATERIALS SCIENCE↗

Mucus-Inspired Tribology, a Sticky Yet Flowing Hydrogel

The mucus blanket can trap foreign particles before they enter the lungs, while at the same time, it flows up to remove these particles. This manifests the dual nature of mucus: sticky, on one hand, and fluid, on the other. Inspired by this function of mucus in the lungs, we designed a mucus simulant which emulates this dual nature. While many existing mucus simulants do not target bioadhesion particularly, poly(vinyl alcohol) (PVA)-based simulants make an exception. Despite their bioadhesion tendency, unlike mucus, they do not gelate. In this study, we added a physical cross-linking agent to PVA in order to add the gelation aspect and to better represent mucous properties. We show that the resultant mucus simulant develops into two regions: a highly sticky region near the surface of a foreign object (we used hydrophobized silicon to mimic the foreign object) and a fluid region far away from that surface. We show that the sticky part can slide past the less sticky part, while the foreign object is stuck to it. However, this mechanism changes with time. At short gelation times, this tendency to separate into two parts is enhanced and the foreign object remains stuck, while the rest of the gel flows. With time, the force required to allow the sticky part to slide over the fluid part is further reduced. However, if the gelation is allowed to proceed for even longer times without disturbance, the force required to slide the two parts past each other increases and the separation between the two parts is inhibited. The hydrogel becomes a sticky goo, which requires a higher force to move or unclog if placed in a duct (much like what happens with mucus in the tracheal duct). We explain the physics of our findings in terms of a competition between the tendency of the polymer to form a gel network and the tendency of the polymer to adsorb onto the foreign object.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High‐Capacity Splitting of Mono‐ and Dibranched Hexane Isomers by a Robust Zinc‐Based Metal–Organic Framework

Abstract High‐efficiency separation of C 6 alkanes, particularly the mono‐ and dibranched isomers by using porous solids, is of paramount significance in the petrochemical industry and, remains a daunting challenge. In this work, we report the complete separation of linear/monobranched hexanes from their dibranched isomers through selective size‐exclusion by a microporous MOF, Zn‐tcpt (H 3 tcpt=2,4,6‐tris(4‐carboxyphenoxy)‐1,3,5‐triazine), with a two‐fold interpenetrated structure of hms nets. Importantly, its adsorption capacity and selectivity are notably higher than those of the previously reported adsorbents that can split mono‐ and dibranched alkane isomers. Dynamic breakthrough measurements verify the excellent separation of C 6 alkane isomers by Zn‐tcpt, and the size‐exclusion based separation mechanism has been confirmed by ab initio materials modeling. The high‐efficiency separation of alkane isomers by Zn‐tcpt can be attributed to its optimal pore dimensions as well as high porosity.

Yu, Liang↗

Thermodynamic modeling of adsorption at the liquid-solid interface

Adsorptive separation techniques are significantly energy efficient in comparison to conventional thermal separation techniques such as distillation. Despite extensive research and development activities undertaken for mixed-gas adsorption, the use of adsorption techniques for the separation of multicomponent liquid mixtures is still limited. A major barrier is the lack of accurate adsorption thermodynamic models, which form the scientific foundation of process simulation of such systems, making the translation to industrial scale challenging. In this work, we have rigorously computed the surface excess of adsorption for six binary liquid mixtures on silica gel at 303 K using the frameworks of the generalized Langmuir isotherm (gL) and the adsorbed solution theory (AST). The six binary liquid mixtures were formed by the pair-wise combinations of four components: benzene, 1,2-dichloroethane, cyclohexane, and n-heptane. We have based our calculations by considering simultaneous equilibria of three phases: saturated vapor phase, bulk liquid phase, and adsorbed phase. Further, the composition of the corresponding saturated vapor phase was estimated by the Nonrandom Two-Liquid activity coefficient model and experimental vapor-liquid equilibria data. The activity coefficients of the adsorbed phase, the central issue of multicomponent adsorption thermodynamics, were calculated using the adsorption Nonrandom Two-Liquid activity coefficient model. Devoid of simplifying assumptions, gL and AST provide rigorous thermodynamic frameworks for adsorption equilibria of multicomponent liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High–Capacity Splitting of Mono– and Dibranched Hexane Isomers by a Robust Zinc–Based Metal–Organic Framework

High-efficiency separation of C 6 alkanes, particularly the mono- and dibranched isomers by using porous solids, is of paramount significance in the petrochemical industry and, remains a daunting challenge. In this work, we report the complete separation of linear/monobranched hexanes from their dibranched isomers through selective size-exclusion by a microporous MOF, Zn-tcpt (H3tcpt=2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine), with a two-fold interpenetrated structure of hms nets. Importantly, its adsorption capacity and selectivity are notably higher than those of the previously reported adsorbents that can split mono- and dibranched alkane isomers. Dynamic breakthrough measurements verify the excellent separation of C 6 alkane isomers by Zn-tcpt, and the size-exclusion based separation mechanism has been confirmed by ab initio materials modeling. Furthermore, the high-efficiency separation of alkane isomers by Zn-tcpt can be attributed to its optimal pore dimensions as well as high porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solution Structure and Hydration Forces between Mica and Hydrophilic Versus Hydrophobic Surfaces

Solid-liquid interfaces are central to a range of interesting phenomena including catalysis, heterogeneous nucleation, water desalination, and biomolecular assembly. While three-dimensional Fast Force Mapping (3D FFM) has emerged as a technique for resolving interfacial solution structure at the molecular scale, key challenges for data interpretation persist, most notably regarding the influence of the probe on the measured structure. Using the mica-water system as a case study, we investigate the effect of hydrophilic and hydrophobic probes on interfacial solution structure measured by 3D FFM. Data from hydrophilic silicon-based probes are in good agreement with molecular dynamics simulations, wherein the innermost water molecules adsorb preferentially at the surface ditrigonal cavity sites followed by two subsequent hydration layers. In contrast, the hydrophobic carbon-based probes detect vertical oscillatory features, but do not show lateral patterning that matches the underlying mica lattice. At high ionic strength, up to six of these oscillatory features are observed extending 2 nm into the solution phase with an average spacing of 0.29 ± (0.04) nm. Further, we also determine that the repulsive hydration force between mica and the hydrophilic probe depends on the nature and concentration of ions in solution. Specifically, solutions with stronger ion-water and ion-ion interactions increase the interfacial viscosity, which results in a stronger repulsive hydration force as the probe approaches the surface. Based on these observations, we present a scheme for controlling the outcomes of particle attachment and aggregation by varying the solution conditions to tune the hydration force.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Adsorption of Rare-Earth Elements in Oligo-Grafted Mesoporous Carbon

Rare-earth elements (REEs) are 17 elements of the periodic table primarily consisting of lanthanides. In modern society, the usage of REEs is ubiquitous in almost all modern gadgets and therefore efficient recovery and separation of REEs are of high importance. Selective adsorption and chelation of REEs in solid sorbents is a unique and sustainable process for their recovery. In this work, single-stranded oligos with 100 units of thymine were grafted onto carboxylated mesoporous carbon to synthesize a sorbent with phosphorus and oxygen functionalities. Additionally, the sorbent was characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and scanning electron microscopy-energy-dispersive X-ray spectroscopy. Three different REEs with varying atomic radii and densities, Lu, Dy, and La, were adsorbed onto the carbon from aqueous solutions. It was observed that the adsorbed amounts increased with the increase in the atomic radius or decrease in the atomic density. Calculation of the distribution coefficients for all the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The L 3 -edge X-ray absorption near-edge structure confirmed a 3+ oxidation state of REEs in the adsorbed phase. Extended X-ray absorption fine structure (EXAFS) confirmed the binding of REEs with oxygen functionalities in the adsorbed phase. The radial distribution functions calculated from the EXAFS data suggest a longer RE–O distance for La compared to those for Lu and Dy. The coordination numbers and Debye–Waller factors have typical values of about 8–9 atoms and 0.01–0.02 Å 2 , respectively.

36 MATERIALS SCIENCE↗

PREPARATION OF CLAY-COATED GLASS SURFACES FOR MICROFLUIDICS-BASED STUDY ON CLAY-FLUID INTERACTIONS

Unique characteristics of clay, even though make any clay abundant shales a good source of adsorbed gas, make them equally difficult to produce. The clay-water interaction can cause significant swelling and fines migration in the shale formation, both of which can significantly impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surface with geomaterials (e.g., calcite, quartz, clay) can represent the physico-chemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. This study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay minerals to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt.% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C). Dynamic flooding tests were carried out with brines on the coated surface to evaluate the stability of the coating. The experiments' outcome indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗

Preparation of illite coated geomaterial microfluidic surfaces: Effect of salinity and heat treatment

Unique characteristics of clay (e.g., high surface area, deficiency in positive charges) make any clay abundant shales a good source of adsorbed gas. However, the presence of clay in porous media can also affect shale rock's producibility. The clay-water interaction can cause significant swelling and fines migration in the formation and impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surfaces with geomaterials (e.g., calcite, Quartz, clay), can represent the physicochemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. Here, this study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C), and the results are compared with an untreated coated surface. Flooding tests were carried out with brines of different salinities on the coated surface to evaluate the stability of the coating. The experimental results indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗

Surface Reactivity of Ag-Modified Ceria to Hydrogen: A Combined Experimental and Theoretical Investigation

We investigate the mechanism of H 2 activation on Ag-modified cerium oxide surfaces, of interest for different catalytic applications. The study is performed on thin epitaxial cerium oxide films, investigated by X-ray photoemission spectroscopy to assess the changes of both the Ag oxidation state and the concentration of Ce 3+ ions, O vacancies, and hydroxyl groups on the surface during thermal reduction cycles in vacuum and under hydrogen exposure. The results are interpreted using density functional theory calculations to model pristine and Ag-modified ceria surfaces. Although the reactivity of ceria toward H 2 oxidation improves when a fraction of Ce cations is substituted with Ag, the concentration of reduced Ce 3+ ions in Ag-modified ceria is found to be lower than in pure ceria under the same conditions. This behavior is observed even though the number of surface oxygen vacancies caused by the thermal treatment under hydrogen exposure is larger for the Ag-modified surface. These results are explained in terms of a change of the oxidation state of the surface Ag, which is able to acquire some of the extra surface electrons created by the oxygen vacancies and the adsorbed hydrogen atoms. Our findings provide new insights into the reactivity of Ag-modified ceria, which has been proposed as a promising alternative to platinum electrodes in electrochemical devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗