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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 H 2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg 2+ 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.
Authors:
 [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:
Report Number(s):
SAND-2015-20819J
Journal ID: ISSN 2155-5435; 558247
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society
Research Org:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metal−organic frameworks; catalysis; C−O bond cleavage; hydrogenolysis; aromatic ethers
OSTI Identifier:
1236475

Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W., El Gabaly, Farid, Sale, Kenneth L., Simmons, Blake A., Singh, Seema, and Allendorf, Mark D.. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds. United States: N. p., Web. doi:10.1021/acscatal.5b02061.
Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W., El Gabaly, Farid, Sale, Kenneth L., Simmons, Blake A., Singh, Seema, & Allendorf, Mark D.. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds. United States. doi:10.1021/acscatal.5b02061.
Stavila, Vitalie, Parthasarathi, Ramakrishnan, Davis, Ryan W., El Gabaly, Farid, Sale, Kenneth L., Simmons, Blake A., Singh, Seema, and Allendorf, Mark D.. 2015. "MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds". United States. doi:10.1021/acscatal.5b02061. https://www.osti.gov/servlets/purl/1236475.
@article{osti_1236475,
title = {MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds},
author = {Stavila, Vitalie and Parthasarathi, Ramakrishnan and Davis, Ryan W. and El Gabaly, Farid and Sale, Kenneth L. and Simmons, Blake A. and Singh, Seema and Allendorf, Mark D.},
abstractNote = {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.},
doi = {10.1021/acscatal.5b02061},
journal = {ACS Catalysis},
number = 1,
volume = 6,
place = {United States},
year = {2015},
month = {11}
}