Pozzolans rich in silica and alumina react with lime to form cementing compounds and are incorporated into portland cement as supplementary cementitious materials (SCMs). However, pozzolanic reactions progress slower than portland cement hydration, limiting their use in modern construction due to insufficient early-age strength. Hence, alternative SCMs that enable faster pozzolanic reactions are necessary including synthetic zeolites, which have high surface areas and compositional purity that indicate the possibility of rapid pozzolanic reactivity. Synthetic zeolites with varying cation composition (Na-zeolite, H-zeolite), SiO2/Al2O3 ratio, and framework type were evaluated for pozzolanic reactivity via Ca(OH)2 consumption using ion exchange and in-situ X-ray diffraction experiments. Na-zeolites exhibited limited exchange reactions with KOH and Ca(OH)2 due to the occupancy of acid sites by Na+ and hydroxyl groups. Meanwhile, H-zeolites readily adsorbed K+ and Ca2+ from a hydroxide solution by exchanging cations with H+ at Brønsted acid sites or cation adsorption at vacant acid sites. By adsorbing cations, the H-zeolite reduced the pH and increased Ca2+ solubility to promote pozzolanic reactions in a system where Ca(OH)2 dissolution/diffusion was a rate limiting factor. High H-zeolite reactivity resulted in 0.8 g of Ca(OH)2 consumed per 1 g of zeolites after 16 h of reaction versus 0.4 g of Ca(OH)2 consumed per 1 g of Na-zeolite. The H-zeolite modulated the pore fluid alkalinity and created a low-density amorphous silicate phase via mechanisms analogous to two-step C-S-H nucleation experiments. Controlling these reaction mechanisms is key to developing next generation pozzolanic cementitious systems with comparable hydration rates to portland cement.
Efficient carbon capture requires the design of new materials with high CO2 selectivity and gas adsorption capacity that can be incorporated into existing industrial processes. Porous liquids (PLs) are promising candidate materials that consist of a nanoporous host and a solvent forming a liquid with permanent porosity based on exclusion of the solvent from the interior of the nanoporous host. Stable PLs are based on solvent-nanoporous host interactions, which can be evaluated through molecular simulations. Here, time- and temperature-dependent density functional theory simulations were performed between four solvents, 2-bromophenol, 4-methylphenol, 2,4-dimethylphenol, and cyclohexanone and the CC13 porous organic cage (POC) as a prototypical PL composition. Overall, minimal reactions occurred in the PL including no changes in the POC structure. Additionally, POC-solvent coordination occurred through interactions of neighboring functional groups such as methyl/bromide and hydroxyl on the solvent molecules with the POC surface. Therefore, the location rather than the number of functional groups on the solvent molecule controls the POC-solvent interactions. Additionally, the POC pore window contracted or expanded up to 8% during solvation, which correlates with the experimental solubility and static solvent-POC binding, where solvents that caused less contraction of the POC pore window increased POC solubility. These results allow for the design of optimized POC-based PL compositions based on solvent-nanoporous host binding and variation in the pore window during solvation.
Porous liquids (PLs), which are solvent-based systems that contain permanent porosity due to the incorporation of a solid porous host, are of significant interest for the capture of greenhouse gases, including CO2. Type 3 PLs formed by using metal-organic frameworks (MOFs) as the nanoporous host provide a high degree of chemical turnability for gas capture. However, pore aperture fluctuation, such as gate-opening in zeolitic imidazole framework (ZIF) MOFs, complicates the ability to keep the MOF pores available for gas adsorption. Therefore, an understanding of the solvent molecular size required to ensure exclusion from MOFs in ZIF-based Type 3 PLs is needed. Through a combined computational and experimental approach, the solvent-pore accessibility of exemplar MOF ZIF-8 was examined. Density functional theory (DFT) calculations identified that the lowest-energy solvent-ZIF interaction occurred at the pore aperture. Experimental density measurements of ZIF-8 dispersed in various-sized solvents showed that ZIF-8 adsorbed solvent molecules up to 2 Å larger than the crystallographic pore aperture. Density analysis of ZIF dispersions was further applied to a series of possible ZIF-based PLs, including ZIF-67, −69, −71(RHO), and −71(SOD), to examine the structure-property relationships governing solvent exclusion, which identified eight new ZIF-based Type 3 PL compositions. Solvent exclusion was driven by pore aperture expansion across all ZIFs, and the degree of expansion, as well as water exclusion, was influenced by ligand functionalization. Using these results, a design principle was formulated to guide the formation of future ZIF-based Type 3 PLs that ensures solvent-free pores and availability for gas adsorption.
Porous liquids (PLs) are an attractive material for gas separation and carbon sequestration due to their permanent internal porosity and high adsorption capacity. PLs that contain zeolitic imidazole frameworks (ZIFs), such as ZIF-8, form PLs through exclusion of aqueous solvents from the framework pore due to its hydrophobicity. The gas adsorption sites in ZIF-8 based PLs are historically unknown; gas molecules could be captured in the ZIF-8 pore or adsorb at the ZIF-8 interface. To address this question, ab initio molecular dynamics was used to predict CO2 binding sites in a PL composed of a ZIF-8 particle solvated in a water, ethylene glycol, and 2-methylimidazole solvent system. Further, the results show that CO2 energetically prefers to reside inside the ZIF-8 pore aperture due to strong van der Waals interactions with the terminal imidazoles. However, the CO2 binding site can be blocked by larger solvent molecules that have greater adsorption interactions. CO2 molecules were unable to diffuse into the ZIF-8 pore, with CO2 adsorption occurring due to binding with the ZIF-8 surface. Therefore, future design of ZIF-based PLs for enhanced CO2 adsorption should be based on the strength of gas binding at the solvated particle surface.
Chemically robust, low-power sensors are needed for the direct electrical detection of toxic gases. Metal-organic frameworks (MOFs) offer exceptional chemical and structural tunability to meet this challenge, though further understanding is needed regarding how coadsorbed gases influence or interfere with the electrical response. To probe the influence of competitive gases on trace NO2 detection in a simulated flue gas stream, a combined structure-property study integrating synchrotron powder diffraction and pair distribution function analyses was undertaken, to elucidate how structural changes associated with gas binding inside Ni-MOF-74 pores correlate with the electrical response from Ni-MOF-74-based sensors. Data were evaluated for 16 gas combinations of N2, NO2, SO2, CO2, and H2O at 50 °C. Fourier difference maps from a rigid-body Rietveld analysis showed that additional electron density localized around the Ni-MOF-74 lattice correlated with large decreases in Ni-MOF-74 film resistance of up to a factor of 6 × 103, observed only when NO2 was present. These changes in resistance were significantly amplified by the presence of competing gases, except for CO2. Without NO2, H2O rapidly (<120 s) produced small (1-3×) decreases in resistance, though this effect could be differentiated from the slower adsorption of NO2 by the evaluation of the MOF’s capacitance. Furthermore, samples exposed to H2O displayed a significant shift in lattice parameters toward a larger lattice and more diffuse charge density in the MOF pore. Evaluating the Ni-MOF-74 impedance in real time, NO2 adsorption was associated with two electrically distinct processes, the faster of which was inhibited by competitive adsorption of CO2. Together, this work points to the unique interaction of NO2 and other specific gases (e.g., H2O, SO2) with the MOF’s surface, leading to orders of magnitude decrease in MOF resistance and enhanced NO2 detection. Understanding and leveraging these coadsorbed gases will further improve the gas detection properties of MOF materials.
Porous liquids (PLs) based on the zeolitic imidazole framework ZIF-8 are attractive systems for carbon capture since the hydrophobic ZIF framework can be solvated in aqueous solvent systems without porous host degradation. However, solid ZIF-8 is known to degrade when exposed to CO2 in wet environments, and therefore the long-term stability of ZIF-8-based PLs is unknown. Through aging experiments, the long-term stability of a ZIF-8 PL formed using the water, ethylene glycol, and 2-methylimidazole solvent system was systematically examined, and the mechanisms of degradation were elucidated. The PL was found to be stable for several weeks, with no ZIF framework degradation observed after aging in N2 or air. However, for PLs aged in a CO2 atmosphere, formation of a secondary phase occurred within 1 day from the degradation of the ZIF-8 framework. From the computational and structural evaluation of the effects of CO2 on the PL solvent mixture, it was identified that the basic environment of the PL caused ethylene glycol to react with CO2 forming carbonate species. These carbonate species further react within the PL to degrade ZIF-8. The mechanisms governing this process involves a multistep pathway for PL degradation and lays out a long-term evaluation strategy of PLs for carbon capture. Additionally, it clearly demonstrates the need to examine the reactivity and aging properties of all components in these complex PL systems in order to fully assess their stabilities and lifetimes.
Decreasing cost of technologies for direct air capture of carbon can be achieved through the design of new materials with high CO2 selectivity that can be incorporated into existing industrial processes. An emerging class of materials for these applications are porous liquids (PLs). PLs are mixtures of porous hosts and solvents with intrinsic porosity due to steric exclusion of solvent from inside the porous host. It is currently unknown how solvent -porous host interactions affect porous host solubility in the bulk solvent. Here, density functional theory simulations were used to investigate interactions between nine solvents and a CC13 porous organic cage (POC). Calculations identified that solvent molecules were the most stable when placed either inside the CC13 POC or in the pore window compared to interfacial binding sites. Structural changes to the CC13 POC correlated with reported experimental solubilities, including expansion of the CC13 POC with solvent molecule infiltration and expansion or contraction of the pore window. Based on these results, new PL design guidelines should include compositions with (1) high concentrations of POCs with flexible cage structures that can expand when solvated and (2) solvent molecule-POC combinations that contract the pore window during solvent molecule-host binding.
Rare-earth terephthalic acid (BDC)-based metal-organic frameworks (MOFs) are promising candidate materials for acid gas separation and adsorption from flue gas streams. However, previous simulations have shown that acid gases (H2O, NO2, and SO2) react with the hydroxyl on the BDC linkers to form protonated acid gases as a potential degradation mechanism. Herein, gas-phase computational approaches were used to identify the formation energies of these secondary protonated acid gases across multiple BDC linker molecules. Formation energies for secondary protonated acid gases were evaluated using both density functional theory (DFT) and correlated wave function methods for varying BDC-gas reaction mechanisms. Upon validation of DFT to reproduce wave function calculation results, rotated conformational linkers and chemically functionalized BDC linkers with −OH, −NH2, and −SH were investigated. The calculations show that the rotational conformation affects the molecule stability. Double-functionalized BDC linkers, where two functional groups are substituted onto BDC, showed varied reaction energies depending on whether the functional groups donate or withdraw electrons from the aromatic system. Based on these results, BDC linker design must balance adsorption performance with degradation via linker dehydrogenation for the design of stable MOFs for acid gas separations.
Direct air capture (DAC) of CO2 is a negative emission technology under development to limit the impacts of climate change. The dilute concentration of CO2 in the atmosphere (~400 ppm) requires new materials for carbon capture with increased CO2 selectivity that is not met with current carbon capture materials. Porous liquids (PLs) are an emerging candidate for carbon capture and consists of a combination of solvents and porous hosts that creates a liquid with permanent porosity. The fundamental mechanisms of carbon capture in a PL are relatively unknown. To uncover these mechanisms, PLs were synthesized consisting of three different zeolitic-imidazolate framework (ZIF-8, ZIF-67, or ZIF-69) porous host in a water/glycol/2-methylimidazole solvent. The most stable composition was based on ZIF-8 and exhibited carbon capture following exposure to CO2. Density functional theory identified a three-step carbon capture mechanism based on (i) reaction of OH- with ethylene glycol in the solution followed by (ii) formation of 2-hydroxyethyl carbonate, which (iii) further react with OH- to form a carbonate species. This mechanism was validated with experimental nuclear magnetic resonance spectroscopy (NMR) to identify the dissolved carbonate phases and the decrease in the pH during CO2 exposure. Deuterated samples of the ZIF-8 PLs were synthesized and analyzed via neutron diffraction at the Spallation Neutron Sources at Oak Ridge National Laboratory. Results identified differences in diffraction for PLs pre- and post-CO2 exposure that will be combined with ab initio molecular dynamics data of the same PL composition to identify how the presence of a solvent-porous host interfaces results in carbon capture.
Understanding the selectivity of metal–organic frameworks (MOFs) to complex acid gas streams will enable their use in industrial applications. Herein, ab initio molecular dynamic simulations (AIMD) were used to simulate ternary gas mixtures (H2O-NO2-SO2) in rare earth 2,5-dihydroxyterephthalic acid (RE-DOBDC) MOFs. Stronger H2O gas-metal binding arose from thermal vibrations in the MOF sterically hindering access of SO2 and NO2 molecules to the metal sites. Gas-gas and gas-linker interactions within the MOF framework resulted in the formation of multiple secondary gas species including HONO, HNO2, NOSO, and HNO3−. Four gas adsorption sites were identified along with a new de-protonation reaction mechanism not observable through experiment. This study not only provides valuable information on competitive gas binding energies in the MOF, it also provides important chemical insights into transient chemical reactions and mechanisms.
Single photon detection (SPD) plays an important role in many forefront areas of fundamental science and advanced engineering applications. In recent years, rapid developments in superconducting quantum computation, quantum key distribution, and quantum sensing call for SPD in the microwave frequency range. We have explored in this LDRD project a new approach to SPD in an effort to provide deterministic photon-number-resolving capability by using topological Josephson junction structures. In this SAND report, we will present results from our experimental studies of microwave response and theoretical simulations of microwave photon number resolving detector in topological Dirac semimetal Cd3As2. These results are promising for SPD at the microwave frequencies using topological quantum materials.
Direct air capture (DAC) of CO2 is one of the negative emission technologies under development to limit the impacts of climate change. The dilute concentration of CO2 in the atmosphere (~400 ppm) requires new materials for carbon capture with increased CO2 selectivity that is not met with current materials. Porous liquids (PLs) are an emerging material that consist of a combination of solvents and porous hosts creating a liquid with permanent porosity. PLs have demonstrated excellent CO2 selectivity, but the features that control how and why PLs selectively capture CO2 is unknown. To elucidate these mechanisms, density functional theory (DFT) simulations were used to investigate two different PLs. The first is a ZIF-8 porous host in a water/glycol/2-methylimidazole solvent. The second is the CC13 porous organic cage with multiple bulky solvents. DFT simulations identified that in both systems, CO2 preferentially bound in the pore window rather than in the internal pore space, identifying that the solvent-porous host interface controls the CO2 selectivity. Additionally, SNL synthesized ZIF-8 based PL compositions. Evaluation of the long-term stability of the PL identified no change in the ZIF-8 crystallinity after multiple agitation cycles, identifying its potential for use in carbon capture systems. Through this project, SNL has developed a fundamental understanding of solvent-host interactions, as well as how and where CO2 binds in PLs. Through these results, future efforts will focus not on how CO2 behaves inside the pore, but on the porous host-solvent interface as the driving force for PL stability and CO2 selectivity.
Rare-earth polynuclear metal-organic frameworks (RE-MOFs) have demonstrated high durability for caustic acid gas adsorption and separation based on gas adsorption to the metal clusters. The metal clusters in the RE-MOFs traditionally contain RE metals bound by μ3-OH groups connected via organic linkers. Recent studies have suggested that these hydroxyl groups could be replaced by fluorine atoms during synthesis that includes a fluorine-containing modulator. Here, a combined modeling and experimental study was undertaken to elucidate the role of metal cluster fluorination on the thermodynamic stability, structure, and gas adsorption properties of RE-MOFs. Through systematic density-functional theory calculations, fluorinated clusters were found to be thermodynamically more stable than hydroxylated clusters by up to 8-16 kJ/mol per atom for 100% fluorination. The extent of fluorination in the metal clusters was validated through a 19F NMR characterization of 2,5-dihydroxyterepthalic acid (Y-DOBDC) MOF synthesized with a fluorine-containing modulator. 19F magic-angle spinning NMR identified two primary peaks in the isotropic chemical shift (δiso) spectra located at -64.2 and -69.6 ppm, matching calculated 19F NMR δiso peaks at -63.0 and -70.0 ppm for fluorinated systems. Calculations also indicate that fluorination of the Y-DOBDC MOF had negligible effects on the acid gas (SO2, NO2, H2O) binding energies, which decreased by only ∼4 kJ/mol for the 100% fluorinated structure relative to the hydroxylated structure. Additionally, fluorination did not change the relative gas binding strengths (SO2 > H2O > NO2). Therefore, for the first time the presence of fluorine in the metal clusters was found to significantly stabilize RE-MOFs without changing their acid-gas adsorption properties.
Metal-organic frameworks (MOFs) have recently been shown to exhibit unique mechanisms of luminescence based on charge transfer between structural units in the framework. These MOFs have the potential to be structural tuned for targeted emission with little or no metal participation. A computationally led, material design and synthesis methodology is presented here that elucidates the mechanisms of light emission in interpenetrated structures comprised of metal centers (M = In, Ga, InGa, InEu) and BTB (1,3,5-Tris(4-carboxyphenyl)benzene) linkers, forming unique luminescent M-BTB MOF frameworks. Gas phase and periodic electronic structure calculations indicate that the intensity of the emission and the wavelength are overwhelmingly controlled by a combination of the number of interacting stacked linkers and their interatomic spacings, respectively. In the MOF, the ionic radii of the metal centers primarily control the expansion or shrinkage of the linker stacking distances. Experimentally, multiple M-BTB-based MOFs are synthesized and their photoluminescence was tested. Experiments validated the modeling by confirming that shifts in the crystal structure result in variations in light emission. Through this material design method, the mechanisms of tuning luminescence properties in interpenetrated M-BTB MOFs have been identified and applied to the design of MOFs with specific wavelength emission based on their structure.
Dirac semimetals have attracted a great deal of current interests due to their potential applications in topological quantum computing, low-energy electronic devices, and single photon detection in the microwave frequency range. Herein are results from analyzing the low magnetic (B) field weak-antilocalization behaviors in a Dirac semimetal Cd3As2 thin flake device. At high temperatures, the phase coherence length lΦ first increases with decreasing temperature (T) and follows a power law dependence of lΦ ∝ T–0.4. Below ~3 K, lΦ tends to saturate to a value of ~180 nm. Another fitting parameter α, which is associated with independent transport channels, displays a logarithmic temperature dependence for T > 3 K, but also tends to saturate below ~3 K. The saturation value, ~1.45, is very close to 1.5, indicating three independent electron transport channels, which we interpret as due to decoupling of both the top and bottom surfaces as well as the bulk. This result, to our knowledge, provides first evidence that the surfaces and bulk states can become decoupled in electronic transport in Dirac semimetal Cd3As2.
A combination of electrodeposition and thermal reduction methods have been utilized for the synthesis of ligand-free FeNiCo alloy nanoparticles through a high-entropy oxide intermediate. These phases are of great interest to the electrocatalysis community, especially when formed by a sustainable chemistry method. This is successfully achieved by first forming a complex five element amorphous FeNiCoCrMn high-entropy oxide (HEO) phase via electrodeposition from a nanodroplet emulsion solution of the metal salt reactants. The amorphous oxide phase is then thermally treated and reduced at 570-600 °C to form the crystalline FeNiCo alloy with a separate CrMnOx cophase. The FeNiCo alloy is fully characterized by scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy elemental analysis and is identified as a face-centered cubic crystal with the lattice constant a = 3.52 Å. The unoptimized, ligand-free FeNiCo NPs activity toward the oxygen evolution reaction is evaluated in alkaline solution and found to have an ∼185 mV more cathodic onset potential than the Pt metal. Beyond being able to synthesize highly crystalline, ligand-free FeNiCo nanoparticles, the demonstrated and relatively simple two-step process is ideal for the synthesis of tailor-made nanoparticles where the desired composition is not easily achieved with classical solution-based chemistries.
Photon detection at microwave frequency is of great interest due to its application in quantum computation information science and technology. Herein are results from studying microwave response in a topological superconducting quantum interference device (SQUID) realized in Dirac semimetal Cd3As2. The temperature dependence and microwave power dependence of the SQUID junction resistance are studied, from which we obtain an effective temperature at each microwave power level. It is observed the effective temperature increases with the microwave power. This observation of large microwave response may pave the way for single photon detection at the microwave frequency in topological quantum materials.
Formation of zeolite supported Ag0 clusters depends on a combination of thermodynamically stable atomic configurations, charge balance considerations, and mobility of species on the surface and within pores. Periodic density functional theory (DFT) calculations were performed to evaluate how the location of Al in the mordenite (MOR) framework and humidity control Ag0 nanocluster formation. Four Al framework sites were studied (T1-T4) and the Al positions in the framework were identified by the shifts in the differential Al⋯Al pair distribution function (PDF). Furthermore, structural information about the Ag0 nanoclusters, such as dangling bonds, can be identified by Ag⋯Ag PDF data. For Ag0 formation in vacuum MOR structures with a Si:Al ratio of 5:1 with Al in the T1 position resulted in the most framework flexibility and the lowest Ag0 nanocluster charge, indicating the best result for formation of charge neutral nanoclusters. When water is present, Al in the T3 and T4 positions results in the formation of the smallest average Ag0 nanoclusters plus greater expansion of the O-T-O bond angle than in vacuum, indicating easier diffusion of the Ag0 nanoclusters to the surface. The presence of Al in 4-membered rings and in pairs indicates favorable MOR structures for formation of single Ag atoms, despite the existence of synthesis challenges. Therefore, Al in the T2 position is the least favorable for Ag0 nanocluster formation in both vacuum and in the presence of water. Al in the T1, T3, and T4 positions provides beneficial effects through framework flexibility and changes in nanocluster size or charge that can be leveraged for design of zeolites for formation of metallic nanoclusters.
This report is a functional review of the radionuclide containment strategies of fluoride-salt-cooled high temperature reactor (FHR), molten salt reactor (MSR) and high temperature gas reactor (HTGR) systems. This analysis serves as a starting point for further, more in-depth analyses geared towards identifying phenomenological gaps that still exist, hindering the creation of a mechanistic source term for these reactor types. As background information to this review, an overview of how a mechanistic source term is created and used for consequence assessment necessary for licensing is provided. How a mechanistic source term is used within the Licensing Modernization Project (LMP) is also provided. Lastly, the characteristics of non-LWR mechanistic source terms are examined. This report does not assess the viability of any software system for use with advanced reactor designs, but instead covers system function requirements. Future work within the Nuclear Energy Advanced Modeling and Simulations (NEAMS) program will address such gaps. This document is an update of SAND 2020-6730. An additional chapter is included as well as edits to original content.
This study relates structure, properties and thermodynamics, through synthesis, characterization and heat of formation measurements of rare earth iridate pyrochlore (RE2Ir2O7; RE = Y, Eu, Pr) crystalline powders. The RE2Ir2O7 phases are synthesized by high temperature solid-state synthesis methods. X-ray diffraction and elemental analysis techniques are utilized to validate the synthesis and enable structural comparisons. Trends in the bond angles indicate deviations from the Y and Eu analogs for the Pr2Ir2O7 phase. High temperature oxide melt solution calorimetry is used to determine the heats of formation of each phase. Breaking the trend expected across the rare earth series, the enthalpy of formation for Pr2Ir2O7 is more exothermic than the anticipated from the Y and Eu analogs.
Reactive gas formation in pores of metal–organic frameworks (MOFs) is a known mechanism of framework destruction; understanding those mechanisms for future durability design is key to next generation adsorbents. Herein, an extensive set of ab initio molecular dynamics (AIMD) simulations are used for the first time to predict competitive adsorption of mixed acid gases (NO2 and H2O) and the in-pore reaction mechanisms for a series of rare earth (RE)-DOBDC MOFs. Spontaneous formation of nitrous acid (HONO) is identified as a result of deprotonation of the MOF organic linker, DOBDC. The unique DOBDC coordination to the metal clusters allows for proton transfer from the linker to the NO2 without the presence of H2O and may be a factor in DOBDC MOF durability. This is a previously unreported mechanisms of HONO formation in MOFs. With the presented methodology, prediction of future gas interactions in new nanoporous materials can be achieved.
Three M-MOF-74 (M = Co, Mg, Ni) metal-organic framework (MOF) thin film membranes have been synthesized through a sensor functionalization method for the direct electrical detection of NO2. The two-step surface functionalization procedure on the glass/Pt interdigitated electrodes resulted in a terminal carboxylate group, with both steps confirmed through infrared spectroscopic analysis. This surface functionalization allowed the MOF materials to grow largely in a uniform manner over the surface of the electrode forming a thin film membrane over the Pt sensing elec-trodes. The growth of each membrane was confirmed through scanning electron microscopy (SEM) and X-ray diffraction analysis. The Ni and Mg MOFs grew as a continuous but non-defect free membrane with overlapping polycrystallites across the glass surface, whereas the Co-MOF-74 grew dis-continuously. To demonstrate the use of these MOF membranes as an NO2 gas sensor, Ni-MOF-74 was chosen as it was consistently fabricated as the best thin and homogenous membrane, as confirmed by SEM. The membrane was exposed to 5 ppm NO2 and the impedance magnitude was observed to decrease 123× in 4 h, with a larger change in impedance and a faster response than the bulk material. Importantly, the use of these membranes as a sensor for NO2 does not require them to be defect-free, but solely continuous and overlapping growth.
Through a combination of single crystal growth, experiments involving in situ deposition of surface adatoms, and complimentary modeling, we examine the electronic transport properties of lithium-decorated ZrTe5 thin films. We observe that the surface states in ZrTe5 are robust against Li adsorption. Both the surface electron density and the associated Berry phase are remarkably robust to adsorption of Li atoms. Fitting to the Hall conductivity data reveals that there exist two types of bulk carriers: those for which the carrier density is insensitive to Li adsorption, and those whose density decreases during initial Li depositions and then saturates with further Li adsorption. We propose this dependence is due to the gating effect of a Li-adsorption-generated dipole layer at the ZrTe5 surface.
Detection and capture of toxic nitrogen oxides (NOx) is important for emissions control of exhaust gases and general public health. The ability to directly electrically detect trace (0.5–5 ppm) NO2 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 NO2 adsorption capacity and specific chemical interaction. Ni-MOF-74 provides the highest sensitivity to NO2; a 725× decrease in resistance at 5 ppm NO2 and detection limit <0.5 ppm, levels relevant for industry and public health. Furthermore, the Ni-MOF-74-based sensor is selective to NO2 over N2, SO2, 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 mm2 with 0.8 mg MOF-74. Finally, this represents a 104–106× 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.
Nenoff, Tina M.; Walton, Ian; Chen, Carmen; Rimsza, Jessica M.; Walton, Krista S.
Adsorption of corrosive SO2 gas occurs in metal-organic frameworks (MOFs) including UiO-66. Improvements in SO2 capacity is obtained through the incorporation of residual modulators in the UiO-66 framework by introducing new binding sites in the material, through residual modulators. Four residual modulators were investigated (acetic acid, trifluoroacetic acid, 3-DMAP acid, cyanoacetic acid), and the UiO-66 framework modulated with cyanoacetic acid exhibited nearly twice the SO2 uptake for the 18:1 modulator/linker synthesis ratio compared with other modulated UiO-66 structures. Density functional theory investigations confirmed that targeted host-guest interactions were maintained after the modulator was incorporated into the framework. The strongest binding energy was between SO2 and cyanoacetic acid, consistent with dynamic SO2 adsorption data, and identified contributions from both the SO2 reacting with the residual modulator and the coordinating linkers. The successful increase in dynamic SO2 capacity illustrates how often-overlooked non-covalent interactions can be used in targeted adsorption applications. Further investigation into weak electrostatic interactions for adsorption properties is also needed to advance the potential selectivity and capacity in the adsorption sphere.
Improving predictive models for noble gas transport through natural materials at the field-scale is an essential component of improving US nuclear monitoring capabilities. Several field-scale experiments with a gas transport component have been conducted at the Nevada National Security Site (Non-Proliferation Experiment, Underground Nuclear Explosion Signatures Experiment). However, the models associated with these experiments have not treated zeolite minerals as gas adsorbing phases. This is significant as zeolites are a common alteration mineral with a high abundance at these field sites and are shown here to significantly fractionate noble gases during field-scale transport. This fractionation and associated retardation can complicate gas transport predictions by reducing the signal-to-noise ratio to the detector (e.g. mass spectrometers or radiation detectors) enough to mask the signal or make the data difficult to interpret. Omitting adsorption-related retardation data of noble gases in predictive gas transport models therefore results in systematic errors in model predictions where zeolites are present.Herein is presented noble gas adsorption data collected on zeolitized and non-zeolitized tuff. Experimental results were obtained using a unique piezometric adsorption system designed and built for this study. Data collected were then related to pure-phase mineral analyses conducted on clinoptilolite, mordenite, and quartz. These results quantify the adsorption capacity of materials present in field-scale systems, enabling the modeling of low-permeability rocks as significant sorption reservoirs vital to bulk transport predictions.
This report is a functional review of the radionuclide containment strategies of fluoride-salt-cooled high temperature reactor (FHR), molten salt reactor (IVISR) and high temperature gas reactor (HTGR) systems. This analysis serves as a starting point for further, more in-depth analyses geared towards identifying phenomenological gaps that still exist, preventing the creation of a mechanistic source term for these reactor types. As background information to this review, an overview of how a mechanistic source term is created and used for consequence assessment necessary for licensing is provided. How mechanistic source term is used within the LMP is also provided. Third, the characteristics of non-LWR mechanistic source terms are examined This report does not assess the viability of any software system for use with advanced reactor designs, but instead covers system function requirements. Future work within the Nuclear Energy Advanced Modeling and Simulations (NEAMS) program will address such gaps.
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 X-ray 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.
The magnetic susceptibility of NOx-loaded RE-DOBDC (rare earth (RE): Y, Eu, Tb, Yb; DOBDC: 2,5-dihydroxyterephthalic acid) metal-organic frameworks (MOFs) is unique to the MOF metal center. RE-DOBDC samples were synthesized, activated, and subsequently exposed to humid NOx. Each NOx-loaded MOF was characterized by powder X-ray diffraction, and the magnetic characteristics were probed by using a VersaLab vibrating sample magnetometer (VSM). Lanthanide-containing RE-DOBDC (Eu, Tb, Yb) are paramagnetic with a reduction in paramagnetism upon adsorption of NOx. Y-DOBDC has a diamagnetic moment with a slight reduction upon adsorption of NOx. The magnetic susceptibility of the MOF is determined by the magnetism imparted by the framework metal center. The electronic population of orbitals contributes to determining the extent of magnetism and change with NOx (electron acceptor) adsorption. Eu-DOBDC results in the largest mass magnetization change upon adsorption of NOx due to more available unpaired f electrons. Experimental changes in magnetic moment were supported by density functional theory (DFT) simulations of NOx adsorbed in lanthanide Eu-DOBDC and transition metal Y-DOBDC MOFs.
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.
Nenoff, Tina M.; Hanna, Sylvia L.; Rademacher, David X.; Hanson, Donald J.; Fairley, Melissa; Olszewski, Alyssa K.; Islamoglu, Timur; Laverne, Jay A.; Farha, Omar K.
Zeolite-supported Ag0 clusters have broad applications from catalysis to medicine, necessitating a mechanistic understanding of the formation of Ag0 clusters in situ. Density functional theory (DFT) simulations have been performed on silver, water, and silver–water clusters in silica mordenite (Si-MOR), to identify the role of the confinement on the structure and energetics of Ag0 cluster formation. The most favorable binding energy in the 12-membered ring (MR) pore of the Si-MOR is a 10–15-atom Ag0 cluster. Computational pair distribution function (PDF) data indicates that the Ag0 and Ag0–H2O clusters formed in vacuum versus in Si-MOR exhibit structural differences. Additionally, when the Ag0 cluster is confined, the density decreases and the surface area increases, hypothesized to be due to the limiting geometry of the 12-MR main channel. An energetic drive toward formation of larger Ag0 clusters was also identified, with hydrated silver atoms generating higher energy structures. In conclusion, this work identifies mechanistic and structural insight into the role of nanoconfinement on formation of Ag0 clusters in mordenite.
Organic linkers in metal-organic framework (MOF) materials exhibit differences in hydrogen bonding (H-bonding), which can alter the geometric, electronic, and optical properties of the MOF. Density functional theory (DFT) simulations were performed on a photoluminescent Y-2,5-dihydroxyterephthalic acid (DOBDC) MOF with H-bonding concentrations between 0 and 100%; the H-bonds were located on both bidentate-and monodentate-bound DOBDC linkers. At 0% H-bond concentration in the framework, the lattice parameters contracted, the density increased, and simulated X-ray diffraction patterns shifted. Comparison with published experimental data identified that Y-DOBDC MOF structures must have a degree of H-bond concentration. The concentration of H-bonds in the system shifted the calculated band gap energy from 2.25 eV at 100% to 3.00 eV at 0%. The band gap energies also indicate a distinction of H-bonds formed on bidentate-coordinated linkers compared to those on monodentate linkers. Additionally, when the calculated optical spectra are compared with experimental data, the ligand-to-ligand charge-transfer luminescence in Y-DOBDC MOFs is expected to result from an average of 20-40% H-bonding with at least 50% of the bidentate linkers containing H-bonding. Therefore, the type of H-bonding within the DOBDC linker determines the electronic structure and the optical absorption of the MOF framework structure. Tuning of the H-bonding in rare-earth MOFs provides an opportunity to control the specific optical and adsorption properties of the MOF framework on the basis of reactions between the linker and the environment.