Abstract: Provided herein are methods of novel methods of synthesizing a metal-organic framework system by vapor-phase appending of a plurality of ligands appended to a metal-organic framework. Also, provided are methods of recycling metal-organic framework systems by detaching the ligand and re-appending the same ligand or appending a different ligand to the metal-organic framework to provide a recycled or repurposed metal-organic framework system.

Abstract: Methods are provided for synthesizing metal organic framework compositions in an aqueous environment and/or in a mixed alcohol/water solvent. The methods can allow for formation of MOF-274 metal organic framework compositions, such as EMM-67 (a mixed metal MOF-274 metal organic framework composition). More generally, the methods can allow for formation of MOF structures that include disalicylate linkers in an aqueous environment and/or in a mixed alcohol/water solvent.

Abstract: Methods are provided for appending amines to metal organic framework (MOF) compositions. In some aspects, the methods can allow for appending of amines in the solution or synthesis solution used for synthesizing a MOF. In such aspects, an amine-appended MOF can be formed without having to first separate and dry the underlying non-amine-appended MOF composition. In other aspects, amines can be appended to an existing MOF composition by exposing the MOF to a suitable amine in a protic solvent, such as water or an alcohol.

Abstract: Metal-organic frameworks are synthesized from either a high concentration synthesis where reaction solutions comprising increased reagent concentrations, or suspensions of reagents which exceed their solubility limit in the reaction solution in a high solids synthesis. In both approaches, the solubility of reagent is maximized by inclusion of a buffer, fixing a nominal pH of the reaction solution to allow metal-organic framework formation. These methods improve yields and scale up of metal-organic frameworks.

Abstract: Fiber compositions are provided that incorporate metal organic framework (MOF) materials into the polymeric matrix of the fiber. The metal organic framework materials can be incorporated by including MOF particles into a “dope” or synthesis solution used to form the fiber. The dope solution can then be used to form fibers that include 5.0 wt % or more of MOF in the resulting polymeric structural material of the fiber, relative to a weight of the fibers. In some aspects, the metal organic framework material can correspond to a MOF with selectivity for adsorption of CO2.

Abstract: Ink compositions are provided for using solvent-based additive manufacturing (SBAM) techniques to form contactor structures and/or structures for use in an adsorption or absorption contactor. Methods forming a contactor using SBAM are also provided. The ink compositions can include a substantial content of adsorbent particles to provide enhanced adsorption by a contactor. Metal organic framework (MOF) structures and zeotype framework structures are examples of types of adsorbent particles that can be incorporated into an ink composition for forming a contactor structure by SBAM. The ink can further include a polymeric component that can serve as the structural component of a polymeric structural material produced by the additive manufacturing method. Such a structural material can correspond to a polymeric material with incorporated adsorbent particles. In some aspects, the polymeric structural material and/or the adsorbent particles can have selectivity for adsorption of CO2 from a process fluid flow.

Abstract: Provided herein are adsorption materials comprising a metal-organic framework comprising metal ions of metals, a plurality of organic linkers and one or more modulator where each modulator forms a localized defect. Each organic linker in the plurality of organic linkers creates a bridge between metal ions. Each modulator is connected to only one metal chain. The adsorption material further comprises one or more ligands. Each ligand in the plurality of ligands can be an amine or other Lewis base (electron donor) appended to a metal ion of the metal-organic framework.

Abstract: Provided herein are adsorption materials comprising a mixed-metal mixed-organic framework comprising metal ions of two or more distinct metals and a plurality of organic linkers. Each organic linker in the plurality of organic linkers is connected to a metal ion. The adsorption material further comprises a plurality of ligands. In an aspect, each respective ligand in the plurality of ligands is an amine or other Lewis base (electron donor) appended to a metal ion in the two of more distinct elements of the mixed-metal organic framework to provide a mixed-metal mixed-organic framework system.

Abstract: Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated via at least two binding sites to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety. The multidentate organic ligand may comprise a reaction product of a vicinal dicarbonyl compound and an amine-substituted salicylic acid to define the first, second and third binding sites. Particular MOFs may comprise 5,59?-(((1E,2E)-ethane-1,2-diylidene)bis-(azaneylylidene))bis(2-hydroxybenzoic acid) as a multidentate organic ligand.

Abstract: Metal-organic framework materials (MOFs) are highly porous entities comprising a multidentate organic ligand coordinated to multiple metal centers, typically as a coordination polymer. Crystallization may be problematic in some instances when secondary binding sites are present in the multidentate organic ligand. Multidentate organic ligands comprising first and second binding sites bridged together with a third binding site comprising a diimine moiety may alleviate these issues, particularly when using a preformed metal cluster as a metal source to form a MOF. Such MOFs may comprise a plurality of metal centers, and a multidentate organic ligand coordinated to the plurality of metal centers to define an at least partially crystalline network structure having a plurality of internal pores, and in which the multidentate organic ligand comprises first and second binding sites bridged together with a third binding site comprising a diimine moiety.

Abstract: Provided herein are methods of novel methods of synthesizing a metal-organic framework system by vapor-phase appending of a plurality of ligands appended to a metal-organic framework. Also, provided are methods of recycling metal-organic framework systems by detaching the ligand and re-appending the same ligand or appending a different ligand to the metal-organic framework to provide a recycled or repurposed metal-organic framework system.

Abstract: A heat transfer (exchange) composition comprising a halide salt matrix having dispersed therein nanoparticles comprising elemental carbon in the absence of water and surfactants, wherein said halide is fluoride or chloride, wherein the halide salt may be an alkali halide salt (e.g., lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, sodium chloride, potassium chloride, rubidium chloride, and eutectic mixtures thereof) or an alkaline earth halide salt (e.g., fluoride or chloride salt of beryllium, magnesium, calcium, strontium, or barium), and wherein the nanoparticles comprising elemental carbon may be solid or hollow, and wherein the composition may further include nanoparticles comprising a fissile material (e.g., U, Th, or Pu) dispersed within the composition. Molten salt reactors (MSRs) containing these heat transfer compositions in coolant loops in thermal exchange with a reactor core, as well operation of such MSRs, are also described.

Abstract: A heat transfer (exchange) composition comprising a halide salt matrix having dispersed therein nanoparticles comprising elemental carbon in the absence of water and surfactants, wherein said halide is fluoride or chloride, wherein the halide salt may be an alkali halide salt (e.g., lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, sodium chloride, potassium chloride, rubidium chloride, and eutectic mixtures thereof) or an alkaline earth halide salt (e.g., fluoride or chloride salt of beryllium, magnesium, calcium, strontium, or barium), and wherein the nanoparticles comprising elemental carbon may be solid or hollow, and wherein the composition may further include nanoparticles comprising a fissile material (e.g., U, Th, or Pu) dispersed within the composition. Molten salt reactors (MSRs) containing these heat transfer compositions in coolant loops in thermal exchange with a reactor core, as well operation of such MSRs, are also described.

Abstract: Methods for removing an oxyanion from an aqueous source containing said oxyanion, comprising contacting said aqueous source with an aqueous-insoluble hydrophobic solution containing an oxyanion extractant compound dissolved in an aqueous-insoluble hydrophobic solvent to result in formation of an oxyanion salt of said extractant compound and extraction of said oxyanion salt into said aqueous-insoluble hydrophobic solution, wherein said extraction results in an extraction affinity (D) of said oxyanion of at least 1, wherein D is the concentration ratio of said oxyanion in the organic phase divided by the concentration of said oxyanion in the aqueous phase; wherein said extractant compound has the following composition: wherein at least one of R1-R10 is or contains a hydrocarbon (R) group containing at least 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

Abstract: A method suitable for use in investigating synthesis conditions for metal-organic frameworks may include: identifying synthesis conditions that includes a first solvent system by which a metal-organic framework is successfully synthesized; and synthesizing the metal-organic framework under substantially the same synthesis conditions but with a second solvent system (or a comparable solvent system) having a difference (Ra) between Hansen solubility parameters of 5 MPa0.5 or less as compared to the first solvent system.

Abstract: Methods for removing an oxyanion from an aqueous source containing said oxyanion, comprising contacting said aqueous source with an aqueous-insoluble hydrophobic solution containing an oxyanion extractant compound dissolved in an aqueous-insoluble hydrophobic solvent to result in formation of an oxyanion salt of said extractant compound and extraction of said oxyanion salt into said aqueous-insoluble hydrophobic solution, wherein said extraction results in an extraction affinity (D) of said oxyanion of at least 1, wherein D is the concentration ratio of said oxyanion in the organic phase divided by the concentration of said oxyanion in the aqueous phase; wherein said extractant compound has the following composition: wherein at least one of R1-R10 is or contains a hydrocarbon (R) group containing at least 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms.

Abstract: A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.

Abstract: A novel metal-organic framework (MOF) templated process for the synthesis of highly porous inorganic sorbents for removing radionuclides, actinides, and heavy metals is disclosed. The highly porous nature of the MOFs leads to highly porous inorganic sorbents (such as oxides, phosphates, sulfides, etc) with accessible surface binding sites that are suitable for removing radionuclides from high level nuclear wastes, extracting uranium from acid mine drainage and seawater, and sequestering heavy metals from waste streams. In some cases, MOFs can be directly used for removing these metal ions as MOFs are converted to highly porous inorganic sorbents in situ.