MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds
Abstract
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.
- Authors:
-
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States); Joint BioEnergy Institute, Emeryville, CA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1236475
- Report Number(s):
- SAND-2015-20819J
Journal ID: ISSN 2155-5435; 558247
- Grant/Contract Number:
- AC04-94AL85000
- Resource 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
- 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
Citation Formats
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., 2015.
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. https://doi.org/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. Mon .
"MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds". United States. https://doi.org/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 = {Mon Nov 23 00:00:00 EST 2015},
month = {Mon Nov 23 00:00:00 EST 2015}
}
Web of Science
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