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