Abstract: The disclosure relates to metal-organic cages which are a class of supramolecular structures comprising organic linkers and transition metal nodes. In an aspect an aluminum-based metal-organic cage (AI-pdc-AA) is disclosed. The cage formation was achieved via solvothermal self-assembly of an aluminum cluster and pyridine-dicarboxylic linker in the presence of acetic acid as a capping agent. The obtained supramolecular structure was characterized by single-crystal X-ray diffraction (SCXRD), thermbgravimetric analysis, and NMR spectroscopies. Based on the single crystal structure and computational analysis, the cage has a 3.7 A diameter electrophilic cavity suitable for the binding of cations, such as cesium (ionic radius 1.81 A). The host-guest interactions were probed with 1 H and 133Cs NM spectroscopies in DMSO, where at low concentrations Cs+ binds to AI-pdc-AA in a 1:1 ratio.

Abstract: Novel crystalline porous materials known as metal-organic frameworks (MOFs) and methods for their synthesis are provided herein. The MOFs include a M6(?3-OH)8(OH)8(?2,?2-(O2C)2cyclam)8 cluster, and a metal atom coordinated to the one or more cyclam of the cluster, wherein M is Zr or Hf, and the metal atom is any one of Cu, Ni, Cr, Ru, Co, and Gd. The MOFs can be used as an adsorbent, alone or in a medium with other components, of CO2. The MOFs can also be used as a catalyst for the transformation of CO2 and epoxides to cyclic carbonates. The MOFs can also be used in the electrochemical catalytic reduction of CO2. The MOFs can also be used for photocatalytic CO2 reduction for the production of carbon-based fossil fuels. The MOFs can also be used for light-induced nitric oxide (NO) release. The MOFs can also be used as magnetic resonance imaging (MRI) agents.

Abstract: Novel crystalline porous materials known as metal-organic frameworks (MOFs) and methods for their synthesis are provided herein. The MOFs include a M6(?3-OH)8(OH)8(?2,?2-(O2C)2cyclam)8 cluster, and a metal atom coordinated to the one or more cyclam of the cluster, wherein M is Zr or Hf, and the metal atom is any one of Cu, Ni, Cr, Ru, Co, and Gd. The MOFs can be used as an adsorbent, alone or in a medium with other components, of CO2. The MOFs can also be used as a catalyst for the transformation of CO2 and epoxides to cyclic carbonates. The MOFs can also be used in the electrochemical catalytic reduction of CO2. The MOFs can also be used for photocatalytic CO2 reduction for the production of carbon-based fossil fuels. The MOFs can also be used for light-induced nitric oxide (NO) release. The MOFs can also be used as magnetic resonance imaging (MRI) agents.

Abstract: Methods and systems for electrochemical reduction of carbon dioxide using advanced aromatic amine heterocyclic catalysts are disclosed. A method for electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C). Step (A) may introduce water to a first compartment of an electrochemical cell. The first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of the electrochemical cell. The second compartment may include a solution of an electrolyte, a catalyst, and a cathode. The catalyst may include at least two aromatic amine heterocycles that are at least one of (a) fused or (b) configured to become electronically conjugated upon one electron reduction. Step (C) may apply an electrical potential between the anode and the cathode in the electrochemical cell sufficient for the cathode to reduce the carbon dioxide to a product mixture.

Abstract: Methods and systems for electrochemical reduction of carbon dioxide using advanced aromatic amine heterocyclic catalysts are disclosed. A method for electrochemical reduction of carbon dioxide may include, but is not limited to, steps (A) to (C). Step (A) may introduce water to a first compartment of an electrochemical cell. Said first compartment may include an anode. Step (B) may introduce carbon dioxide to a second compartment of said electrochemical cell. Said second compartment may include a solution of an electrolyte, a catalyst, and a cathode. Said catalyst may include at least two aromatic amine heterocycles that are at least one of (a) fused or (b) configured to become electronically conjugated upon one electron reduction. Step (C) may apply an electrical potential between said anode and said cathode in said electrochemical cell sufficient for said cathode to reduce said carbon dioxide to a product mixture.