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Title: Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2

Abstract

Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.

Inventors:
; ;
Publication Date:
Research Org.:
The Regents Of The University Of Michigan, Ann Arbor, MI (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1264476
Patent Number(s):
9,393,548
Application Number:
14/139,184
Assignee:
The Regents Of The University Of Michigan (Ann Arbor, MI) DOESC
DOE Contract Number:
SC0004888
Resource Type:
Patent
Resource Relation:
Patent File Date: 2013 Dec 23
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Matzger, Adam J., Liu, Baojian, and Wong-Foy, Antek G.. Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2. United States: N. p., 2016. Web.
Matzger, Adam J., Liu, Baojian, & Wong-Foy, Antek G.. Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2. United States.
Matzger, Adam J., Liu, Baojian, and Wong-Foy, Antek G.. 2016. "Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2". United States. doi:. https://www.osti.gov/servlets/purl/1264476.
@article{osti_1264476,
title = {Rapid and enhanced activation of microporous coordination polymers by flowing supercritical CO.sub.2},
author = {Matzger, Adam J. and Liu, Baojian and Wong-Foy, Antek G.},
abstractNote = {Flowing supercritical CO.sub.2 is used to activate metal organic framework materials (MOF). MOFs are activated directly from N,N-dimethylformamide (DMF) thus avoiding exchange with a volatile solvent. Most MCPs display increased surface areas directly after treatment although those with coordinatively unsaturated metal centers benefit from additional heating.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 7
}

Patent:

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  • The present invention is an apparatus for extracting organic compounds from solid materials. A generator vessel has a removable closure for receiving a solid or liquid solvent which is heated with a resistive heating element to a gaseous or supercritical phase. The removable closure is unencumbered because the side wall is penetrated with an outlet for the gaseous or supercritical solvent. The generator vessel further has a pressure transducer that provides an electronic signal related to pressure of the gaseous or supercritical solvent. The apparatus of the present invention further includes at least one extraction cell having a top andmore » a bottom and a wall extending therebetween, wherein the bottom is sealably penetrated by an inlet for gaseous or supercritical solvent received through a manifold connected to the outlet, the top having an easy-open removable closure cap, and the wall having an outlet port. Finally, a permeable sample cartridge is included for holding the solid materials and to provide radial-flow of the extraction fluid, which is placed within the extraction cell.« less
  • Described is a method of reducing CO.sub.2 to CO using visible radiation and plasmonic photocatalysts. The method includes contacting CO.sub.2 with a catalyst, in the presence of H.sub.2, wherein the catalyst has plasmonic photocatalytic reductive activity when exposed to radiation having a wavelength between 380 nm and 780 nm. The catalyst, CO.sub.2, and H.sub.2 are exposed to non-coherent radiation having a wavelength between 380 nm and 780 nm such that the catalyst undergoes surface plasmon resonance. The surface plasmon resonance increases the rate of CO.sub.2 reduction to CO as compared to the rate of CO.sub.2 reduction to CO without surfacemore » plasmon resonance in the catalyst.« less
  • Disclosed herein is a three-dimensional coordination complex that includes a plurality of inorganic centers; a plurality of a first bis(bidentate) linker; and a plurality of a second bis(bidentate) linker, where the first and the second bis(bidentate) linkers are have different lengths, and the bidentate binding sites on each linker face in opposite directions on an axis.
  • In a decade, many porous coordination polymers have been synthesized, providing a variety of properties ranging from storage, separation and exchange of guests in their cavities, magnetism, conductivity and catalysis by their frameworks. Recent advent of flexible porous coordination polymers, which exhibit elastic guest accommodation in contrast to rigid three-dimensional (3-D) frameworks of conventional porous materials, have acquired a position as a new class of porous materials. Such flexible porous properties induce highly selective guest accommodation and magnetic modulation, which could now be a unique class of practical materials. In this review, we introduce recent flexible porous coordination polymers (3-17)more » and their functional properties, categorizing with the four types of pores with framework deformation.« less
  • Four three-dimensional lanthanide coordination polymers with reversible structural interconversions, [Ln{sub 2}(Hpdc){sub 2}(C{sub 2}O{sub 4})(H{sub 2}O){sub 4}]{sub n}·2nH{sub 2}O [Ln=Sm (1), Eu (2), Tb (3) and Dy (4)], have been synthesized by hydrothermal reactions of lanthanide nitrates with 3,5-pyrazoledicarboxylic (H{sub 3}pdc) and oxalic acids. It is noteworthy that there is an in situ reaction in 1, in which H{sub 3}pdc was decomposed into (ox){sup 2−} with Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. These compounds are isostructural and crystallized in the monoclinic P2{sub 1}/c space group. The Ln(III) ions are eight-coordinated with dodecahedron coordination geometry. These polyhedra are linked by oxalate groupsmore » to form 1D zigzag chain, which are further connected by 3,5-pyrazoledicarboxylate to extend similar 3D frameworks with channels along c-axis in 1–4. These coordination polymers display the characteristic emission bands of the Ln(III) ions in the solid state and possess good thermal stabilities. - Graphical abstract: Four 3D microporous lanthanide coordination polymers with reversible structural interconversion have been synthesized. They exhibit characteristic emission bands of the lanthanide ions and possess great thermal stability. - Highlights: • Four lanthanide coordination polymers have been hydrothermal synthesized. • There is an in situ reaction in 1 in which H{sub 3}pdc was decomposed into (ox){sup 2−} with the Cu(II)–Sm(III) synergistic effect under hydrothermal conditions. • TGA and XRD studies reveal that upon hydration–dehydration, compounds 1–4 undergo a reversible structural interconversion process through a cooling-heating cycle. • Compounds 1–4 exhibit characteristic lanthanide-centered luminescence.« less