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

Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

doi:10.1021/acscatal.5b02061

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

Journal Article · Mon Nov 23 00:00:00 EST 2015 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5b02061· OSTI ID:1236475

Stavila, Vitalie ^[1]; Parthasarathi, Ramakrishnan ^[2]; Davis, Ryan W. ^[1]; El Gabaly, Farid ^[1]; Sale, Kenneth L. ^[2]; Simmons, Blake A. ^[2]; Singh, Seema ^[2]; Allendorf, Mark D. ^[1]

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)

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.

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Research Organization:: Sandia National Lab. (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1236475

Report Number(s):: SAND-2015-20819J; 558247

Journal Information:: ACS Catalysis, Vol. 6, Issue 1; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 74 works

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

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