Spent nuclear fuel contains 129I, which is of particular concern due to its very long half‐life, its potential mobility in the environment, and its deleterious effect on human health. In spent fuel reprocessing schemes under consideration, a gas stream containing 129I2 would be passed through a bed of Ag‐loaded zeolites such as Ag–mordenite (Ag–MOR). We have investigated the use of a low‐temperature sintering bismuth–silicon–zinc‐oxide glass powder mixed with either AgI or AgI–MOR to produce dense glass composite material waste forms that can be processed at 550°C, where AgI volatility is low. We have demonstrated that when fine silver flake is added to the mixture, any adsorbed I2 released during heating of AgI–MOR reacts with the silver to form AgI in situ. Furthermore, we have shown that mixtures of the glass with the AgI–MOR or AgI are durable in aqueous environments. Finally, we have developed a process to fabricate core/shell waste forms where the core of AgI–MOR or AgI and glass is encased in a shell of glass that protects the core from contact with the environment. To prevent cracking of the shell due to thermal expansion mismatch between the core and shell, amorphous silica was added to the shell to form a composite with a lower coefficient of thermal expansion.

Metal–organic frameworks (MOFs) NU-1000 and UiO-66 are herein exposed to two different gamma irradiation doses and dose rates and analyzed to determine the structural features that affect their stability in these environments. MOFs have shown promise for the capture and sensing of off-gases at civilian nuclear energy reprocessing sites, nuclear waste repositories, and nuclear accident locations. However, little is understood about the structural features of MOFs that contribute to their stability levels under the ionizing radiation conditions present at such sites. This study is the first of its kind to explore the structural features of MOFs that contribute to their radiolytic stability. Both NU-1000 and UiO-66 are MOFs that contain Zr metal-centers with the same metal absorption cross section. However, the two MOFs exhibit different linker connectivities, linker aromaticities, node densities, node connectivities, and interligand separations. In this study, NU-1000 and UiO-66 were exposed to high (423.3 Gy/min, 23 min, and 37 s) and low (0.78 Gy/min, 4320 min) dose rates of 60Co gamma irradiation. NU-1000 displayed insignificant radiation damage under both dose rates due to its high linker connectivity, low node density, and low node connectivity. However, low radiation dose rates caused considerable damage to UiO-66, a framework with lower aromaticity and smaller interligand separation. Results suggest that chronic, low-radiation environments are more detrimental to Zr MOF stability than acute, high-radiation conditions.

Detection and capture of toxic nitrogen oxides (NO x) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5-5 ppm) NO 2 by a metal-organic framework (MOF)-74-based sensor at relatively low temperatures (50 °C) is demonstrated via changes in electrical properties of M-MOF-74, M = Co, Mg, Ni. The magnitude of the change is ordered Ni > Co > Mg and explained by each variant's NO 2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO 2 ; a 725× decrease in resistance at 5 ppm NO 2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO 2 over N 2 , SO 2 , and air. Linking this fundamental research with future technologies, the high impedance of MOF-74 enables applications requiring a near-zero power sensor or dosimeter, with the active material drawing <15 pW for a macroscale device 35 mm 2 with 0.8 mg MOF-74. This represents a 10 4-10 6 × decrease in power consumption compared to other MOF sensors and demonstrates the potential for MOFs as active components for long-lived, near-zero power chemical sensors in smart industrial systems and the internet of things.

A novel metal−organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE−Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV−Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal Xray diffraction (SCXRD), scanning electron microscopy−energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

In the pursuit of highly stable and selective metal− organic frameworks (MOFs) for the adsorption of caustic acid gas species, an entire series of rare earth MOFs have been explored. Each of the MOFs in this series (RE-DOBDC; RE