Abstract: Metal organic frameworks are provided that exhibit a reversible phase change from a collapsed state to an expanded state. Due to this material property, these adsorbents exhibit stepped isotherms that have relevance in chemical storage and separations. The metal organic framework is M(LDP), where M is a metal selected from the group of Zn, Fe or Co and L is a ligand selected from the group of 1,4-benzenedipyrazolate (H2BDP), 2,5-pyridinedipyrazolate (H2PyDP), 2,5-pyrimidinedipyrazolate (H2PymDP), 2,5-pyrazinedipyrazolate (H2PyzDP), and 3,6-pyridazinedipyrazolate (H2PydDP). The step pressure position in the isotherm was changed by using nitrogen instead of carbon in the ring allowing for tunable aromatic interactions.

Abstract: A system and method for acid gas separations using porous frameworks of metal atoms coordinatively bound to polytopic linkers that are functionalized with basic nitrogen ligands that expose nitrogen atoms to the pore volumes forming adsorption sites. Adjacent basic nitrogen ligands on the metal-organic framework can form an ammonium from one ligand and a carbamate from the other. The formation of one ammonium carbamate pair influences the formation of ammonium carbamate on adjacent adsorption sites. Adsorption of acid gas at the adsorption sites form covalently linked aggregates of more than one ammonium carbamate ion pair. The acid gas adsorption isotherm can be tuned to match the step position with the partial pressure of acid gas in the gas mixture stream through manipulation of the metal-ligand bond strength by selection of the ligand, metal and polytopic linker materials.

Abstract: The disclosure relates to composite membranes for selective separation and processing of fluids and industrial applications.

Abstract: The disclosure relates to membranes and membranes systems for the separation of trace components in a fluid mixture.

Abstract: The electrochemical carbon dioxide reduction reaction (CO2RR) provides opportunities to synthesize value-added products from this greenhouse gas in a sustainable manner. Efficient catalysts for this reaction are provided that selectively drive CO2 reduction over the thermodynamic and kinetically competitive hydrogen evolution reaction (HER) in organic or aqueous electrolytes. The catalysts are metal-polypyridyl coordination complexes of a redox non-innocent terpyridine-based pentapyridine ligand and a first-row transition metal. The metal-ligand cooperativity in [Fe(tpyPY2Me)]2+ drives the electrochemical reduction of CO2 to CO at low overpotentials with high selectivity for CO2RR (>90%).

Abstract: An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a CO2 adsorption capacity of greater than 2.50 mmol/g at 150 mbar CO2 at 40° C. Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg2(dobpdc), where dobpdc4? is 4,4?-dioxidobiphenyl-3,3?-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

Abstract: Primary, secondary (1°,2°) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for CO2 capture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimzing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4?=4,4?-dioxido-[1,1?:4?,1?-terphenyl]-3,3?-dicarboxylate), yields diamine-appended adsorbents displaying a single CO2 adsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4?=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single CO2 adsorption step with bulky diamines.

Abstract: An adsorbate-selective metal organic framework includes a transition metal; and a plurality of organic molecules coordinated to the transition metal so as to preserve open coordination sites for selectively adsorbing molecules that have low-lying ?* orbitals. The transition metal has a lowest energy spin state in the presence of the selectively adsorbed molecules that are strongly bonding to the transition metal through ?-donating interactions which is different than the lowest energy spin state in the absence of these adsorbed molecules. The transition metal has also a lowest energy spin state in the presence of non-selected molecules that are weakly bonding to the transition metal through ?- and/or ?-accepting and/or donating interactions.

Abstract: An adsorption material is disclosed that comprises a metal-organic framework and a plurality of ligands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a CO2 adsorption capacity of greater than 2.50 mmol/g at 150 mbar CO2 at 40° C. Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propanediamine. An example of the metal-organic framework is Mg2(dobpdc), where dobpdc4? is 4,4?-dioxidobiphenyl-3,3?-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

Abstract: A permanently porous vanadium(II)-containing metal-organic framework (MOF) with vanadium(II) centers and methods for synthesis of such MOF frameworks are provided. Methods for using such compounds to selectively react with N2 over CH4 are provided. In the synthetic methods, a vanadium source, such as VY2(tmeda)2, where Y is a halogen and tmeda is N,N,N?,N?-tetramethylethane-1,2-diamine and a H2(ligand) are reacted in the presence of acid in a solvent at between 110° C. and 130° C. to form an intermediate product. The intermediate product is collected and washed with a washing agent, such as DMF and acetonitrile, and the vanadium(II) based MOF is activated by heating the washed intermediate product to at least 160° C. under dynamic vacuum.

Abstract: Ether-thioether functionalized porous aromatic framework (PAF) polymers provide high selectivity for iron(II) and iron(III) adsorption in aqueous samples.

Abstract: Primary, secondary (1°,2°) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for CO2 capture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimzing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4?=4,4?-dioxido-[1,1?:4?,1?-terphenyl]-3,3?-dicarboxylate), yields diamine-appended adsorbents displaying a single CO2 adsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4?=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single CO2 adsorption step with bulky diamines.

Abstract: The disclosure provides for polymer membranes which comprise metal organic frameworks, methods of making therein, and methods of use thereof, including in gas separation.

Abstract: Methods of synthesizing crystalline metal-organic frameworks (MOFs) comprising polytopic organic linkers and cations, where each linker is connected to two or more cations, are provided. In the disclosed methods, the linkers are reacted with a compound of formula MnXm, where M is cationic Be, Mg, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Cd, or Hf, X is anionic, n and m are integers. The reacting is buffered by a buffer devoid of metal coordinating functionality when the pKa of the anion is below a threshold related to the lowest pKa of the linker. The reacting is optionally not buffered when the pKa of the anion is at or above this threshold. The disclosed methods lead to product phase MOF in which crystal growth is controlled leading to control over molecular diffusion.

Abstract: The electrochemical carbon dioxide reduction reaction (CO2RR) provides opportunities to synthesize value-added products from this greenhouse gas in a sustainable manner. Efficient catalysts for this reaction are provided that selectively drive CO2 reduction over the thermodynamic and kinetically competitive hydrogen evolution reaction (HER) in organic or aqueous electrolytes. The catalysts are metal-polypyridyl coordination complexes of a redox non-innocent terpyridine-based pentapyridine ligand and a first-row transition metal. The metal-ligand cooperativity in [Fe(tpyPY2Me)]2+ drives the electrochemical reduction of CO2 to CO at low overpotentials with high selectivity for CO2RR (>90%).

Abstract: Olsalazine (H4olz), a prodrug of the anti-inflammatory 5-aminosalicylic acid, is used as a ligand to synthesize a suite of M(H2olz) and M2(olz) materials, where M is a dication (e.g. Mg, Ca, Sr, Fe, Co, Ni, Cu, Zn). A family of metal olsalazine coordination polymers, coordination solids, and metal organic frameworks are described, which include 1-, 2-, and 3-dimensional structures. The materials resist degradation at acidic pH and release olsalazine preferentially at neutral pH. The mesoporous M2(olz) frameworks exhibit high surface areas with hexagonal pore apertures that are approximately 27 ? in diameter and contain coordinatively unsaturated metal sites. Biologically active molecules containing a Lewis-basic functional group can be grafted directly to the open metal sites of the frameworks. Dissolution of the frameworks under physiological conditions releases olsalazine (H4olz) and the grafted molecules so that multiple therapeutic components can be delivered together at different rates.

Abstract: Polyamines with lengths carefully tailored to the framework dimensions are appended to metal-organic frameworks such as Mg2(dobpdc) (dobpdc4-=4,4?-dioxidobiphenyl-3,3?-dicarboxylate) with the desired loading of one polyamine per two metal sites. The polyamine-appended materials show step-shaped adsorption and desorption profiles due to a cooperative CO2 adsorption/desorption mechanism. Several disclosed polyamine-appended materials exhibit strong ability to capture CO2 from various compositions. Increased stability of amines in the framework has been achieved using high molecular weight polyamine molecules that coordinate multiple metal sites in the framework. The preparation of these adsorbents as well as their characterization are provided.

Abstract: An adsorption material is disclosed that comprises a metal-organic framework and a plurality of Hgands. The metal-organic framework comprising a plurality of metal ions. Each respective ligand in the plurality of ligands is amine appended to a respective metal ion in the plurality of metal ions of the metal-organic framework. Each respective ligand in the plurality of ligands comprises a substituted 1,3-propanediamine. The adsorbent has a CO2 adsorption capacity of greater than 2.50 mmol/g at 150 mbar CO2 at 40° C., Moreover, the adsorbent is configured to regenerate at less than 120° C. An example ligand is diamine 2,2-dimethyl-1,3-propane-diamine. An example of the metal-organic framework is Mg2(dobpdc), where dobpdc4? is 4,4?-dioxidobiphenyl-3,3?-dicarboxylate. Example applications for the adsorption material are removal of carbon dioxide from flue gas and biogasses.

Abstract: Primary, secondary (1º,2º) alkylethylenediamine- and alkylpropylenediamine-appended variants of metal-organic framework are provided for CO2 capture applications. Increasing the size of the alkyl group on the secondary amine enhances the stability to diamine volatilization from the metal sites. Two-step adsorption/desorption profiles are overcome by minimizing steric interactions between adjacent ammonium carbamate chains. For instance, the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4?=4,4?-dioxido-[1,1?:4?,1?-terphenyl]-3,3?-dicarboxylate), yields diamine-appended adsorbents displaying a single CO2 adsorption step. Further, use of the isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4?=3,3-dioxidobiphenyl-4,4-dicarboxylate, pc=para-carboxylate) also leads to a single CO2 adsorption step with bulky diamines.

Abstract: A system and method for acid gas separations using porous frameworks of metal atoms coordinatively bound to polytopic linkers that are functionalized with basic nitrogen ligands that expose nitrogen atoms to the pore volumes forming adsorption sites. Adjacent basic nitrogen ligands on the metal-organic framework can form an ammonium from one ligand and a carbamate from the other. The formation of one ammonium carbamate pair influences the formation of ammonium carbamate on adjacent adsorption sites. Adsorption of acid gas at the adsorption sites form covalently linked aggregates of more than one ammonium carbamate ion pair. The acid gas adsorption isotherm can be tuned to match the step position with the partial pressure of acid gas in the gas mixture stream through manipulation of the metal-ligand bond strength by selection of the ligand, metal and polytopic linker materials.