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This content will become publicly available on November 23, 2016

Title: MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.
 [1] ;  [2] ;  [1] ;  [1] ;  [2] ;  [2] ;  [2] ;  [1]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States); Joint BioEnergy Institute, Emeryville, CA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 2155-5435; 558247
Grant/Contract Number:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2155-5435
American Chemical Society
Research Org:
Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY metal−organic frameworks; catalysis; C−O bond cleavage; hydrogenolysis; aromatic ethers