Publications

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As an analogue of the mineral pollucite (CsAlSi2O6), CsTiSi2O6.5 is a potential host phase for radioactive Cs. However, as ¹³⁷Cs and ¹³⁵Cs transmute to ¹³⁷Ba and ¹³⁵Ba, respectively, through the beta decay, it is essential to study the structure and stability of this phase upon Cs → Ba substitution. In this work, two series of Ba/Ti-substituted samples, CsxBa(1-x)/2TiSi2O6.5 and CsxBa1-xTiSi2O7-0.5x, (x = 0.9 and 0.7), were synthesized by higherature crystallization from their respective precursors. Synchrotron X-ray diffraction and Rietveld analysis reveal that while CsxBa(1-x)/2TiSi2O6.5 samples are phase-pure, CsxBa1-xTiSi2O7-0.5x samples contain Cs3x/(2+x)Ba(1-x)/(2+x)TiSi2O6.5 pollucites (i.e., also two-Cs-to-one-Ba substitution) and a secondary phase, fresnoite (Ba2TiSi2O8). Thus, the CsxBa1-xTiSi2O7-0.5x series is energetically less favorable than CsxBa(1-x)/2TiSi2O6.5. To study the stability systematics of CsxBa(1-x)/2TiSi2O6.5 pollucites, higherature calorimetric experiments were performed at 973 K with or without the lead borate solvent. Enthalpies of formation from the constituent oxides (and elements) have thus been derived. The results show that with increasing Ba/(Cs + Ba) ratio, the thermodynamic stability of these phases decreases with respect to their component oxides. Hence, from the energetic viewpoint, continued Cs → Ba transmutation tends to destabilize the parent silicotitanate pollucite structure. However, the Ba-substituted pollucite co-forms with fresnoite (which incorporates the excess Ba), thereby providing viable ceramic waste forms for all the Ba decay products.

Two large size Glass Composite Material (GCM) waste forms containing AgI-MOR were fabricated. One contained methyl iodide-loaded AgI-MOR that was received from Idaho National Laboratory (INL, Test 5, Beds 1 – 3) and the other contained iodine vapor loaded AgIMOR that was received from Oak Ridge National Laboratory (ORNL, SHB 2/9/15 ). The composition for each GCM was 20 wt% AgI-MOR and 80 wt% Ferro EG2922 low sintering temperature glass along with enough added silver flake to prevent any I2 loss during the firing process. The silver flake amounts were 1.2 wt% for the GCM with the INL AgI-MOR and 3 wt% for the GCM contained the ORNL AgI-MOR. The GCMs, nominally 100 g, were first uniaxially pressed to 6.35 cm (2.5 inch) diameter disks then cold isostatically pressed, before firing in air to 550°C for 1hr. They were cooled slowly (1°C/min) from the firing temperature to avoid any cracking due to temperature gradients. The final GCMs were ~5 cm in diameter (~2 inches) and non-porous with densities of ~4.2 g/cm³. X-ray diffraction indicated that they consisted of the amorphous glass phase with small amounts of mordenite and AgI. Furthermore, the presence of the AgI was confirmed by X-ray fluorescence. Methodology for the scaled up production of GCMs to 6 inch diameter or larger is also presented.

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Membranes are essential components for the removal of greenhouse gases during fuel generation processes, such as hydrogen production, but simultaneous permeability and selectivity is difficult to obtain. This has now been achieved in ultrathin membranes that use the size-selective porosity of metal–organic frameworks to separate CO₂ from H₂.

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Computational screening of metal-organic framework (MOF) materials for selective oxygen adsorption from air is used to identify new sorbents for oxyfuel combustion process feedstock streams. A comprehensive study on the effect of MOF metal chemistry on gas binding energies in two common but structurally disparate MOFs has been undertaken. Dispersion-corrected density functional theory (DFT) methods were used to calculate the oxygen and nitrogen binding energies with each of 14 metals, respectively, substituted into two MOF series, M2(dobdc) and M3(btc)2. The accuracy of DFT methods was validated by comparing trends in binding energy with experimental gas sorption measurements. A periodic trend in oxygen binding energies was found, with greater oxygen binding energies for early transition-metal-substituted MOFs compared to late transition metal MOFs; this was independent of MOF structural type. The larger binding energies were associated with oxygen binding in a side-on configuration to the metal, with concomitant lengthening of the O-O bond. In contrast, nitrogen binding energies were similar across the transition metal series, regardless of both MOF structural type and metal identity. Taken together, these findings suggest that early transition metal MOFs are best suited to separating oxygen from nitrogen and that the MOF structural type is less important than the metal identity.

Here we describe the homogeneous substitution of Mn, Fe and Co at various levels into a prototypical metal-organic framework (MOF), namely Cu-BTC (HKUST-1), and the effect of that substitution on preferential gas sorption. Using a combination of density functional theory (DFT) calculations, postsynthetic metal substitutions, materials characterization, and gas sorption testing, we demonstrate that the identity of the metal ion has a quantifiable effect on their oxygen and nitrogen sorption properties at cryogenic temperatures. An excellent correlation is found between O₂/N₂ selectivities determined experimentally at 77 K and the difference in O₂ and N₂ binding energies calculated from DFT modeling data: Mn > Fe > Co > Cu. Room temperature gas sorption studies were also performed and correlated with metal substitution. The Fe-exchanged sample shows a significantly higher nitrogen isosteric heat of adsorption at temperatures close to ambient conditions (273 K - 298 K) as compared to all other metals studied, indicative of favorable interactions between N₂ and coordinatively unsaturated Fe metal centers. Furthermore, differences in gas adsorption results at cryogenic and room temperatures are evident; they are explained by comparing experimental results with DFT binding energies (0 K) and room temperature Grand Canonical Monte Carlo simulations.

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The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent. Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. The MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.

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Herein, we study the durability of the Sandia Bi-Si oxide Glass Composite Material (GCM) waste form when formulated with different weight percent levels of AgI-MOR. The post-iodine exposure AgI-MOR material was provided to SNL by ORNL. Durability results for the GCM fabricated with 22 and 25% AgI-MOR indicate releases of Ag and I at the same low rates as 15% AgI-MOR GCM, and by the same mechanism. Iodine and Ag release is controlled by the low solubility of an amorphous, hydrated silver iodide, not by the surface-controlled dissolution of I₂- loaded Ag-Mordenite. Based on this data, we postulate that much higher loading levels of AgIMOR are probable in this GCM waste form, and limits will govern by retention of mechanical integrity of the GCM versus the solubility of silver iodide.

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Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I₂) to form AgI. However the mechanisms for organoiodine capture are not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent.