Search

Injecting fluids into deep underground geologic structures is a critical component to development of long-term strategies for managing greenhouse gas emissions and facilitating energy extraction operations. Recently, we reported that metal–organic frameworks are low-frequency, absorptive-acoustic metamaterial that may be injected into the subsurface to enhance geophysical monitoring tools used to track fluids and map complex structures. A key requirement for this nanotechnology deployment is transportability through porous geologic media without being retained by mineral-fluid interfaces. We used flow-through column studies to estimate transport and retention properties of five different polymer-coated MIL-101(Cr) nanoparticles (NP) in siliceous porous media. When negatively charged polystyrene sulfonate coated nanoparticles (NP-PSS-70K) were transported in 1 M NaCl, only about 8.4% of nanoparticles were retained in the column. Nanoparticles coated with polyethylenimine (NP-PD1) exhibited significant retention (> 50%), emphasizing the importance of complex nanoparticle-fluid-rock interactions for successful use of nanofluid technologies in the subsurface. Nanoparticle transport experiments revealed that nanoparticle surface characteristics play a critical role in nanoparticle colloidal stability and as well the transport. [ABSTRACT FROM AUTHOR]

The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core-shell nanostructured electrocatalysts (core-shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core-shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core-shell Co@NC-anode water electrolyzer delivers 10 mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2-anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2-anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core-shell Co@NC-anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core-shell electrocatalysts with enriched active centers. [ABSTRACT FROM AUTHOR]

The mixed-metal strategy, by which a MOF framework with two different metal nodes was prepared, was utilized with MOF-74 for potential adsorption chiller applications. The Ni salt precursor was partially replaced during synthesis with the relatively inexpensive Zn salt. The bimetallic MOF-74 containing only a fraction of Ni was shown to provide efficient H2O adsorption performance, while utilizing the more inexpensive Zn salt thus significantly mitigated the material costs of industrial scale synthesis/applications. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs) have recently attracted enormous interest over the past few years in energy storage and gas separation, yet there have been few reports for adsorption cooling applications. Adsorption cooling technology is an established alternative to mechanical vapor compression refrigeration systems and is an excellent alternative in industrial environments where waste heat is available. We explored the use of MOFs that have very high mass loading and relatively low heats of adsorption, with certain combinations of refrigerants to demonstrate a new type of highly efficient adsorption chiller. Computational fluid dynamics combined with a system level lumped-parameter model have been used to project size and performance for chillers with a cooling capacity ranging from a few kW to several thousand kW. These systems rely on stacked micro/mini-scale architectures to enhance heat and mass transfer. Recent computational studies of an adsorption chiller based on MOFs suggests that a thermally-driven coefficient of performance greater than one may be possible, which would represent a fundamental breakthrough in performance of adsorption chiller technology. Presented herein are computational and experimental results for hydrophyilic and fluorophilic MOFs. [ABSTRACT FROM PUBLISHER]

The metal organic framework, MOF-74(Ni), was synthesized in a continuous flow microwave-assisted reactor obtaining a high space-time yield (~90 g h−1 L−1) and 96.5% conversion of reagents. Separation of the nucleation and growth steps was performed by using uniform and rapid microwave heating to induce nucleation, which allowed a substantial increase in conversion for shorter reaction times under mild pressure. High yields were achieved in minutes, as opposed to days for typical batch syntheses, with excellent control over the material's properties due to more uniform nucleation, and the separation of the nucleation and growth steps. Optimization of the microwave reactor parameters led to improvements in MOF-74(Ni) crystallinity, reagent conversion, and production rates. Differences in MOF-74(Ni) crystallinity were observed as smaller grains were formed when higher microwave zone temperatures were used. Crystallinity differences led to different final adsorption properties and surface areas. Herein we show that a continuous high space-time yield synthesis of MOF-74(Ni) allows control over nucleation using microwave heating. [ABSTRACT FROM AUTHOR]

A flexible metal–organic framework constructed from a flexible linker is shown to possess the capability of separating mixtures of polar compounds (propanol isomers) by exploiting the differences in the saturation capacities of the constituents. Transient breakthrough simulations show that these sorption-based separations are in favor of the component with higher saturation capacity. [ABSTRACT FROM AUTHOR]

Zeolite HOU-2 (LTA type) is prepared with the highest silica content (Si/Al = 2.1) reported for Na-LTA zeolites without the use of an organic structure-directing agent. The rational design of Si-rich zeolites has the potential to improve their thermal stability for applications in catalysis, gas storage, and selective separations. [ABSTRACT FROM AUTHOR]

A detailed mechanism, based on densityfunctional theory calculationsand simulation, is presented outlining the formation of the secondarybuilding unit (SBU) of MIL-101, a chromium terephthalate metal organicframework (MOF). Formation of the metal core and of the SBU is keyto MOF nucleation, the rate-limiting step in the synthesis processof many MOFs. A series of reactions that lead to the formation ofthe SBU of MIL-101 is proposed in this work. The highest barrier (∼35kcal/mol) involves the formation of a dimetal-linker intermediateand high to low spin transition as a third Cr-linker moiety joinsto form a three metal-linker group joined by a central oxygen. Theterephthalate linkers play an important, key mechanistic role withthe carboxylates first joining chromium atoms prior to the formationof bridging oxygens. Subsequent to metal core formation, stepwiselinker addition reactions generate different assembly pathways dueto structural isomers that are limited by the removal of water moleculesin the first chromium coordination shell. A simple kinetic model basedon transition state theory gave a rate of SBU formation similar toa reported rate of MOF nucleation. The least energy path was identifiedwith all linkers on the same face of the metal center added first.These first steps in developing a modeling framework for SBU formationwill hopefully lay the groundwork for future comprehensive predictivemodels of the full MOF framework structure assembly and synthesisconditions required to support the self-assembly process. [ABSTRACT FROM AUTHOR]

In this review, we describe recent efforts to systematically study nano-structured metal organic frameworks (MOFs), also known as metal organic heat carriers, with particular emphasis on their application in heating and cooling processes. We used both molecular dynamics and grand canonical Monte Carlo simulation techniques to gain a molecular-level understanding of the adsorption mechanism of gases in these porous materials. We investigated the uptake of various gases such as refrigerants R12 and R143a. We also evaluated the effects of temperature and pressure on the uptake mechanism. Our computed results compared reasonably well with available measurements from experiments, thus validating our potential models and approaches. In addition, we investigated the structural, diffusive and adsorption properties of different hydrocarbons in Ni2(dhtp). Finally, to elucidate the mechanism of nanoparticle dispersion in condensed phases, we studied the interactions among nanoparticles in various liquids, such asn-hexane, water and methanol. [ABSTRACT FROM PUBLISHER]

Metal-organic frameworks (MOFs) are one of the widely investigated materials of 21st century due to their unique properties such as structural tailorability, controlled porosity, and crystallinity. These exceptional properties make them promising candidates for various applications including gas adsorption and storage, separation, and catalysis. However, commercial applications of MOFs produced by conventional methods including solvothermal or hydrothermal synthesis are rather limited or restricted because they often produce fine powders. The use of MOF powders for industrial applications often results in pressure drop problems similar to the case with zeolites and limited robustness against water. To realize these materials for practical applications, densification of MOFs (by increasing pellet density) is routinely employed to form pellets, extrudates or beads to improve the overall density, volumetric adsorption, mechanical and thermal properties. However, the improvements come with some drawbacks such as reduction in overall porosity, surface area, and gravimetric adsorption capacity. Thus, optimizing the properties of densified MOF's by tuning the pellet density is very crucial for realizing these materials for industrial applications. Methods that increase the packing density in MOFs (for example by intentional interpenetration, etc.), which is different from pellet density, is not the scope of this review. In this review, the properties and applications of densified MOFs with different metal clusters and organic linkers are discussed. [ABSTRACT FROM AUTHOR]

The magnetic susceptibility of synthesized magnetite (Fe3O4) microspheres was found to decline after the growth of a metal-organic framework (MOF) shell on the magnetite core. Detailed structural analysis of the core-shell particles using scanning electron microscopy, transmission electron microscopy, atom probe tomography, and 57Fe-Mössbauer spectroscopy suggests that the distribution of MOF precursors inside the magnetic core resulted in the oxidation of the iron oxide core. [ABSTRACT FROM AUTHOR]