Herbert T. Schaef

In Situ One-Step Synthesis of Hierarchical Nitrogen-Doped Porous Carbon for High-Performance Supercapacitors

A hierarchically structured nitrogen-doped porous carbon is prepared from a nitrogen-containing isoreticular metal-organic framework (IRMOF-3) using a self-sacrificial templating method. IRMOF-3 itself provides the carbon and nitrogen content as well as the porous structure. For high carbonization temperatures (950 °C), the carbonized MOF required no further purification steps, thus eliminating the need for solvents or acid. Nitrogen content and surface area are easily controlled by the carbonization temperature. The nitrogen content decreases from 7 to 3.3 at % as carbonization temperature increases from 600 to 950 °C. There is a distinct trade-off between nitrogen content, porosity, and defects in the carbon structure. Carbonized IRMOFs are evaluated as supercapacitor electrodes. For a carbonization temperature of 950 °C, the nitrogen-doped porous carbon has an exceptionally high capacitance of 239 F g(-1). In comparison, an analogous nitrogen-free carbon bears a low capacitance of 24 F g(-1), demonstrating the importance of nitrogen dopants in the charge storage process. The route is scalable in that multi-gram quantities of nitrogen-doped porous carbons are easily produced.

Gas-induced transformation and expansion of a non-porous organic solid

Organic solids composed by weak van der Waals forces are attracting considerable attention owing to their potential applications in gas storage, separation and sensor applications. Herein we report a gas-induced transformation that remarkably converts the high-density guest-free form of a well-known organic host (p-tert-butylcalix[4]arene) to a low-density form and vice versa, a process that would be expected to involve surmounting a considerable energy barrier. This transformation occurs despite the fact that the high-density form is devoid of channels or pores. Gas molecules seem to diffuse through the non-porous solid into small lattice voids, and initiate the transition to the low-density kinetic form with approximately 10% expansion of the crystalline organic lattice, which corresponds to absorption of CO2 and N2O (refs 4,5). This suggests the possibility of a more general phenomenon that can be exploited to find more porous materials from non-porous organic and metal-organic frameworks that possess void space large enough to accommodate the gas molecules.

In Situ Molecular Spectroscopic Evidence for CO2 Intercalation into Montmorillonite in Supercritical Carbon Dioxide

The interaction of anhydrous supercritical CO(2) (scCO(2)) with both kaolinite and ~1W (i.e., close to but less than one layer of hydration) calcium-saturated montmorillonite was investigated under conditions relevant to geologic carbon sequestration (50 °C and 90 bar). The CO(2) molecular environment was probed in situ using a combination of three novel high-pressure techniques: X-ray diffraction, magic angle spinning nuclear magnetic resonance spectroscopy, and attenuated total reflection infrared spectroscopy. We report the first direct evidence that the expansion of montmorillonite under scCO(2) conditions is due to CO(2) migration into the interlayer. Intercalated CO(2) molecules are rotationally constrained and do not appear to react with waters to form bicarbonate or carbonic acid. In contrast, CO(2) does not intercalate into kaolinite. The findings show that predicting the seal integrity of caprock will have complex dependence on clay mineralogy and hydration state.

In Situ X-ray Diffraction Study of Na+ Saturated Montmorillonite Exposed to Variably Wet Super Critical CO2

Reactions involving variably hydrated super critical CO(2) (scCO(2)) and a Na saturated dioctahedral smectite (Na-STX-1) were examined by in situ high-pressure X-ray diffraction at 50 °C and 90 bar, conditions that are relevant to long-term geologic storage of CO(2). Both hydration and dehydration reactions were rapid with appreciable reaction occurring in minutes and near steady state occurring within an hour. Hydration occurred stepwise as a function of increasing H(2)O in the system; 1W, 2W-3W, and >3W clay hydration states were stable from ~2-30%, ~31-55 < 64%, and ≥ ~71% H(2)O saturation in scCO(2), respectively. Exposure of sub 1W clay to anhydrous scCO(2) caused interlayer expansion, not contraction as expected for dehydration, suggesting that CO(2) intercalated the interlayer region of the sub 1W clay, which might provide a secondary trapping mechanism for CO(2). In contrast, control experiments using pressurized N(2) and similar initial conditions as in the scCO(2) study, showed little to no change in the d(001) spacing, or hydration states, of the clay. A salient implication for cap rock integrity is that clays can dehydrate when exposed to wet scCO(2). For example, a clay in the ~3W hydration state could collapse by ~3 Å in the c* direction, or ~15%, if exposed to scCO(2) at less than or equal to about 64% H(2)O saturation.

Near-Field Performance Assessment for a Low-Activity Waste Glass Disposal System: Laboratory Testing to Modeling Results

Abstract Reactive chemical transport simulations of glass corrosion and radionuclide release from a low-activity waste (LAW) disposal system were conducted out to times in excess of 20 000 yr with the subsurface transport over reactive multiphases (STORM) code. Time and spatial dependence of glass corrosion rate, secondary phase formation, pH, and radionuclide concentration were evaluated. The results show low release rates overall for the LAW glasses such that performance objectives for the site will be met by a factor of 20 or more. Parameterization of the computer model was accomplished by combining direct laboratory measurements, literature data (principally thermodynamic data), and parameter estimation methods.

Fluorocarbon adsorption in hierarchical porous frameworks

Metal-organic frameworks comprise an important class of solid-state materials and have potential for many emerging applications such as energy storage, separation, catalysis and bio-medical. Here we report the adsorption behaviour of a series of fluorocarbon derivatives on a set of microporous and hierarchical mesoporous frameworks. The microporous frameworks show a saturation uptake capacity for dichlorodifluoromethane of >4 mmol g(-1) at a very low relative saturation pressure (P/Po) of 0.02. In contrast, the mesoporous framework shows an exceptionally high uptake capacity reaching >14 mmol g(-1) at P/Po of 0.4. Adsorption affinity in terms of mass loading and isosteric heats of adsorption is found to generally correlate with the polarizability and boiling point of the refrigerant, with dichlorodifluoromethane > chlorodifluoromethane > chlorotrifluoromethane > tetrafluoromethane > methane. These results suggest the possibility of exploiting these sorbents for separation of azeotropic mixtures of fluorocarbons and use in eco-friendly fluorocarbon-based adsorption cooling.

Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal-Organic Framework

The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal-organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe-network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.

In Situ Study of CO2 and H2O Partitioning between Na–Montmorillonite and Variably Wet Supercritical Carbon Dioxide

Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this study, in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy were used to investigate the swelling/shrinkage and H2O/CO2 sorption of Na(+)-exchanged montmorillonite, Na-SWy-2, as the clay is exposed to variably hydrated supercritical CO2 (scCO2) at 50 °C and 90 bar. Measured d001 values increased in stepwise fashion and sorbed H2O concentrations increased continuously with increasing percent H2O saturation in scCO2, closely following previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show H2O and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types of H2O and CO2 with distinct chemical environments. Based on the absorbance of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, the sorbed CO2 concentration increases dramatically at sorbed H2O concentrations from 0 to 4 mmol/g. Sorbed CO2 then sharply decreases as sorbed H2O increases from 4 to 10 mmol/g. With even higher sorbed H2O concentrations as saturation of H2O in scCO2 was approached, the concentration of sorbed CO2 decreased asymptotically. Two models, one involving space filling and the other a heterogeneous distribution of integral hydration states, are discussed as possible mechanisms for H2O and CO2 intercalations in montmorillonite. The swelling/shrinkage of montmorillonite could affect solid volume, porosity, and permeability of shales. Consequently, the results may aid predictions of shale caprock integrity in large-scale GCS as well as methane transmissivity in enhanced gas recovery operations.

CO2 Sorption to Subsingle Hydration Layer Montmorillonite Clay Studied by Excess Sorption and Neutron Diffraction Measurements

Geologic storage of CO(2) requires that the caprock sealing the storage rock is highly impermeable to CO(2). Swelling clays, which are important components of caprocks, may interact with CO(2) leading to volume change and potentially impacting the seal quality. The interactions of supercritical (sc) CO(2) with Na saturated montmorillonite clay containing a subsingle layer of water in the interlayer region have been studied by sorption and neutron diffraction techniques. The excess sorption isotherms show maxima at bulk CO(2) densities of ≈ 0.15 g/cm(3), followed by an approximately linear decrease of excess sorption to zero and negative values with increasing CO(2) bulk density. Neutron diffraction experiments on the same clay sample measured interlayer spacing and composition. The results show that limited amounts of CO(2) are sorbed into the interlayer region, leading to depression of the interlayer peak intensity and an increase of the d(001) spacing by ca. 0.5 Å. The density of CO(2) in the clay pores is relatively stable over a wide range of CO(2) pressures at a given temperature, indicating the formation of a clay-CO(2) phase. At the excess sorption maximum, increasing CO(2) sorption with decreasing temperature is observed while the high-pressure sorption properties exhibit weak temperature dependence.

Forsterite [Mg2SiO4)] Carbonation in Wet Supercritical CO2: An in Situ High-Pressure X-ray Diffraction Study

Mechanisms controlling mineral stabilities in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss carbonation reactions occurring with forsterite (Mg(2)SiO(4)) exposed to variably wet supercritical CO(2) (scCO(2)). Transformation reactions were tracked by in situ high-pressure X-ray diffraction in the presence of scCO(2) containing dissolved water. Under modest pressures (90 bar) and temperatures (50 °C), scCO(2) saturated with water converted >70 wt % forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO(3) · 3H(2)O), and magnesite (MgCO(3)) after 72 h. However, comparable tests with scCO(2) at only partial water saturation showed a faster carbonation rate but significantly less nesquehonite formation and no evidence of the anhydrous form (MgCO(3)). The presence and properties of a thin water film, observed by in situ infrared (IR) spectroscopy and with isotopically labeled oxygen ((18)O), appears to be critical for this silicate mineral to carbonate in low water environments. The carbonation products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to enable better predictions of the long-term fate of geologically stored CO(2).