Abstract: A permanently porous vanadium(II)-containing metal-organic framework (MOF) withvanadium(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: Achieving the selective and reversible adsorption of CO2 from humid, low partial pressures streams such as the flue gas resulting from the combustion of natural gas in combined cycle power plants (4% CO2) is challenging due to the need for high thermal, oxidative, and hydrolytic stability as well as moderate regeneration conditions to reduce the energy of adsorption/desorption cycling. Appending cyclic primary, secondary diamines, exemplified by 2-(aminomethyl)piperidine (2-ampd), to the metal-organic frameworks Mg2(dobpdc) (dobpdc4?=4,4-dioxidobiphenyl-3,3-dicarboxylate), Mg2(dotpdc) (dotpdc4?=4,4?-dioxido-[1,1?:4?,1?-terphenyl]-3,3?-dicarboxylate) or Mg2(pc-dobpdc) (pc-dobpdc4?=dioxidobiphenyl-4,4?-dicarboxylate) produces adsorbents of the classes EMM-44, EMM-45, and EMM-46, respectively, that display step-shaped adsorption of CO2 at the partial pressures required for 90% capture from natural gas flue gas at temperatures up to or exceeding 60° C.

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 provides for adsorbents with stepped isotherms for gas storage applications.

Abstract: The disclosure provides for polymer networks having the general structure: that can effectively serve as a single-ion conducting electrolyte.

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: A method of selective detection of a concentration of a metal ion species in a subject is provided in which a biofluid sample is obtained from the subject. The biofluid sample is exposed to a functionalized porous aromatic polymer. The polymer selectively captures and concentrates the metal ion species from the biofluid. Subsequently, the biofluid is washed from the polymer. The polymer is then exposed to a solution comprising a colorimetric indicator that extracts the metal ion species from the washed polymer thereby changing a color of the solution as a function of an amount of the metal ion species in the polymer. The concentration of the metal ion species in the subject is then spectroscopically determined from the color of the solution.

Abstract: Functionalized metal-organic framework adsorbents with ligands containing basic nitrogen groups such as alkylamines and alkyldiamines appended to the metal centers and method of isolating carbon dioxide from a stream of combined gases and carbon dioxide partial pressures below approximately 1 and 1000 mbar. The adsorption material has an isosteric heat of carbon dioxide adsorption of greater than ?60 kJ/mol at zero coverage using a dual-site Langmuir model.

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: 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: 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: 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: Achieving the selective and reversible adsorption of CO2 from humid, low partial pressures streams such as the flue gas resulting from the combustion of natural gas in combined cycle power plants (4% CO2) is challenging due to the need for high thermal, oxidative, and hydrolytic stability as well as moderate regeneration conditions to reduce the energy of adsorption/desorption cycling. Appending cyclic primary, secondary diamines, exemplified by 2-(aminomethyl)piperidine (2-ampd), to the metal-organic frameworks Mg2(dobpdc) (dobpdc4?=4,4-dioxidobiphenyl-3,3-dicarboxylate), Mg2(dotpdc) (dotpdc4?=4,4?-dioxido-[1,1?:4?,1?-terphenyl]-3,3?-dicarboxylate) or Mg2(pc-dobpdc) (pc-dobpdc4?=dioxidobiphenyl-4,4?-dicarboxylate) produces adsorbents of the classes EMM-44, EMM-45, and EMM-46, respectively, that display step-shaped adsorption of CO2 at the partial pressures required for 90% capture from natural gas flue gas at temperatures up to or exceeding 60° C.

Abstract: Functionalized metal-organic framework adsorbents with ligands containing basic nitrogen groups such as alkylamines and alkyldiamines appended to the metal centers and method of isolating carbon dioxide from a stream of combined gases and carbon dioxide partial pressures below approximately 1 and 1000 mbar. The adsorption material has an isosteric heat of carbon dioxide adsorption of greater than ?60 kJ/mol at zero coverage using a dual-site Langmuir model.

Abstract: The disclosure provides for metal organic frameworks (MOFs) that are selective adsorbents for aromatic hydrocarbons, devices comprising the MOFs thereof, and methods using the MOFS thereof for separating and/or storing aromatic hydrocarbons.

Abstract: The disclosure provides for adsorbents with stepped isotherms for gas storage applications.

Abstract: The disclosure provides for diamine-appended metal-organic frameworks (MOFs), methods of making thereof, and methods of use thereof.

Abstract: The disclosure provides for metal organic frameworks (MOFs) which comprise a plurality of redox-active metals or metal ions that are linked together by a plurality of dioxide-benzenedicarboxylate-based organic linking ligands. The disclosure further provides for the use of these MOFs in variety of applications, including catalyzing the oxidization of various hydrocarbons to higher oxidation states.

Abstract: The disclosure provides for Metal-Organic Frameworks comprising M2 (m-dobdc)-based cores, and methods of use thereof, including gas separation, gas storage, sensing, and other applications utilizing a high density of exposed metal cation sites.