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Title: Metal-organic framework catalysts for selective cleavage of aryl-ether bonds

Abstract

The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.

Inventors:
;
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1373909
Patent Number(s):
9,718,748
Application Number:
14/991,734
Assignee:
Sandia Corporation SNL-A
DOE Contract Number:
AC04-94AL85000
Resource Type:
Patent
Resource Relation:
Patent File Date: 2017 Jan 08
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Allendorf, Mark D., and Stavila, Vitalie. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds. United States: N. p., 2017. Web.
Allendorf, Mark D., & Stavila, Vitalie. Metal-organic framework catalysts for selective cleavage of aryl-ether bonds. United States.
Allendorf, Mark D., and Stavila, Vitalie. 2017. "Metal-organic framework catalysts for selective cleavage of aryl-ether bonds". United States. doi:. https://www.osti.gov/servlets/purl/1373909.
@article{osti_1373909,
title = {Metal-organic framework catalysts for selective cleavage of aryl-ether bonds},
author = {Allendorf, Mark D. and Stavila, Vitalie},
abstractNote = {The present invention relates to methods of employing a metal-organic framework (MOF) as a catalyst for cleaving chemical bonds. In particular instances, the MOF results in selective bond cleavage that results in hydrogenolyzis. Furthermore, the MOF catalyst can be reused in multiple cycles. Such MOF-based catalysts can be useful, e.g., to convert biomass components.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2017,
month = 8
}

Patent:

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  • The disclosure provides methods for the use of open metal frameworks to catalyze coupling reactions.
  • Two new Zn(II)–organic compounds, [Zn(muco)(dbds){sub 2}(H{sub 2}O){sub 2}] (1) and [Zn(muco)(dbs)] (2) (where, muco=trans, trans-muconate dianion, dbds=4,4′-dipyridyldisulfide and dbs=4,4′-dipyridylsulfide) have been synthesized from same precursors but at two different temperatures. Both the compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR spectroscopy, thermal analysis and photoluminescence studies. Compound 1 prepared at room temperature possesses a molecular structure extended to 2D supramolecular network through (H–O…H) hydrogen-bonding interactions. Compound 2, obtained at high temperature (100 °C) shows a 3-fold interpenetrating 3D framework constituted by an in situ generated dbs linker by the cleavage of S–S and C–Smore » bonds of dbds linker. Thus, the influence of reaction temperature on the formation of two structural phases has been demonstrated. Both 1 and 2 exhibit ligand based luminescence emission owing to n→π⁎ and π→π⁎ transitions and also high thermal stabilities. - Graphical abstract: The influence of temperature on the formation of two structural phases, a 2D supramolecular network and a 3D 3-fold interpenetrating framework has been demonstrated and their luminescence emission is measured. - Highlights: • Two new Zn(II)–organic compounds were synthesized by tuning reaction temperatures. • Temperature induced in situ generation of dbs linker has been observed. • The compounds exhibit high thermal stability and luminescence emission properties. • The effect of temperature on structure, dimension and topology has been presented.« less
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  • Here, lignin is a combinatorial polymer comprising monoaromatic units that are linked via covalent bonds. Although lignin is a potential source of valuable aromatic chemicals, its recalcitrance to chemical or biological digestion presents major obstacles to both the production of second-generation biofuels and the generation of valuable coproducts from lignin's monoaromatic units. Degradation of lignin has been relatively well characterized in fungi, but it is less well understood in bacteria. A catabolic pathway for the enzymatic breakdown of aromatic oligomers linked via β-aryl ether bonds typically found in lignin has been reported in the bacterium Sphingobium sp. SYK-6. Here, wemore » present x-ray crystal structures and biochemical characterization of the glutathione-dependent β-etherases, LigE and LigF, from this pathway. The crystal structures show that both enzymes belong to the canonical two-domain fold and glutathione binding site architecture of the glutathione S-transferase family. Mutagenesis of the conserved active site serine in both LigE and LigF shows that, whereas the enzymatic activity is reduced, this amino acid side chain is not absolutely essential for catalysis. The results include descriptions of cofactor binding sites, substrate binding sites, and catalytic mechanisms. Because β-aryl ether bonds account for 50–70% of all interunit linkages in lignin, understanding the mechanism of enzymatic β-aryl ether cleavage has significant potential for informing ongoing studies on the valorization of lignin.« less
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