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Title: 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:
 [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:
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}
}

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Works referenced in this record:

Applications of metal–organic frameworks in heterogeneous supramolecular catalysis
journal, January 2014

  • Liu, Jiewei; Chen, Lianfen; Cui, Hao
  • Chemical Society Reviews, Vol. 43, Issue 16, p. 6011-6061
  • DOI: 10.1039/C4CS00094C

Porous Metal–Organic Frameworks for Heterogeneous Biomimetic Catalysis
journal, February 2014

  • Zhao, Min; Ou, Sha; Wu, Chuan-De
  • Accounts of Chemical Research, Vol. 47, Issue 4, p. 1199-1207
  • DOI: 10.1021/ar400265x

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks with exposed metal sites
journal, January 2011

  • Colombo, Valentina; Galli, Simona; Choi, Hye Jin
  • Chemical Science, Vol. 2, Issue 7, p. 1311-1319
  • DOI: 10.1039/c1sc00136a

Water Stability and Adsorption in Metal–Organic Frameworks
journal, September 2014

  • Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S.
  • Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612
  • DOI: 10.1021/cr5002589

Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal–Organic Frameworks
journal, March 2014

  • Aijaz, Arshad; Xu, Qiang
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8, p. 1400-1411
  • DOI: 10.1021/jz5004044

Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation
journal, April 2014

  • Guo, Zhiyong; Xiao, Chaoxian; Maligal-Ganesh, Raghu V.
  • ACS Catalysis, Vol. 4, Issue 5, p. 1340-1348
  • DOI: 10.1021/cs400982n

Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids
journal, April 2014

  • Barta, Katalin; Ford, Peter C.
  • Accounts of Chemical Research, Vol. 47, Issue 5, p. 1503-1512
  • DOI: 10.1021/ar4002894

Metal Organic Framework Catalysis: Quo vadis ?
journal, December 2013

  • Gascon, Jorge; Corma, Avelino; Kapteijn, Freek
  • ACS Catalysis, Vol. 4, Issue 2, p. 361-378
  • DOI: 10.1021/cs400959k

Reversible Hydrogen Storage by NaAlH 4 Confined within a Titanium-Functionalized MOF-74(Mg) Nanoreactor
journal, October 2012

  • Stavila, Vitalie; Bhakta, Raghunandan K.; Alam, Todd M.
  • ACS Nano, Vol. 6, Issue 11
  • DOI: 10.1021/nn304514c

Engineering Metal Organic Frameworks for Heterogeneous Catalysis
journal, August 2010

  • Corma, A.; García, H.; Llabrés i Xamena, F. X.
  • Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655
  • DOI: 10.1021/cr9003924

Advances in Coal Gasification, Hydrogenation, and Gas Treating for the Production of Chemicals and Fuels
journal, October 2013

  • Higman, Christopher; Tam, Samuel
  • Chemical Reviews, Vol. 114, Issue 3, p. 1673-1708
  • DOI: 10.1021/cr400202m

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals
journal, February 2012

  • Ruppert, Agnieszka M.; Weinberg, Kamil; Palkovits, Regina
  • Angewandte Chemie International Edition, Vol. 51, Issue 11, p. 2564-2601
  • DOI: 10.1002/anie.201105125

Catalytic nickel nanoparticles embedded in a mesoporous metal–organic framework
journal, January 2010

  • Park, Young Kwan; Choi, Sang Beom; Nam, Hye Jin
  • Chemical Communications, Vol. 46, Issue 18, p. 3086-3088
  • DOI: 10.1039/c000775g

Large-Pore Apertures in a Series of Metal-Organic Frameworks
journal, May 2012


Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals
journal, May 2014

  • Wang, Lisa J.; Deng, Hexiang; Furukawa, Hiroyasu
  • Inorganic Chemistry, Vol. 53, Issue 12, p. 5881-5883
  • DOI: 10.1021/ic500434a

Bio-inspired MOF-based Catalysts for Lignin Valorization
report, September 2014

  • Allendorf, Mark D.; Stavila, Vitalie; Ramakrishnan, Parthasarathi
  • DOI: 10.2172/1159323

Titanium Nitride-Nickel Nanocomposite as Heterogeneous Catalyst for the Hydrogenolysis of Aryl Ethers
journal, January 2014

  • Molinari, Valerio; Giordano, Cristina; Antonietti, Markus
  • Journal of the American Chemical Society, Vol. 136, Issue 5, p. 1758-1761
  • DOI: 10.1021/ja4119412

Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin
journal, April 2012


A Heterogeneous Nickel Catalyst for the Hydrogenolysis of Aryl Ethers without Arene Hydrogenation
journal, December 2012

  • Sergeev, Alexey G.; Webb, Jonathan D.; Hartwig, John F.
  • Journal of the American Chemical Society, Vol. 134, Issue 50, p. 20226-20229
  • DOI: 10.1021/ja3085912

Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions
journal, July 2010

  • Meilikhov, Mikhail; Yusenko, Kirill; Esken, Daniel
  • European Journal of Inorganic Chemistry, Vol. 2010, Issue 24, p. 3701-3714
  • DOI: 10.1002/ejic.201000473

Asymmetric Hydrogenation of Heteroarenes and Arenes
journal, November 2011

  • Wang, Duo-Sheng; Chen, Qing-An; Lu, Sheng-Mei
  • Chemical Reviews, Vol. 112, Issue 4, p. 2557-2590
  • DOI: 10.1021/cr200328h

Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores
journal, August 2008

  • Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J.
  • Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871
  • DOI: 10.1021/ja8036096

Noble Gas Adsorption in Metal–Organic Frameworks Containing Open Metal Sites
journal, May 2014

  • Perry, John J.; Teich-McGoldrick, Stephanie L.; Meek, Scott T.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 22, p. 11685-11698
  • DOI: 10.1021/jp501495f

Hydrogen storage properties and neutron scattering studies of Mg2(dobdc)—a metal–organic framework with open Mg2+ adsorption sites
journal, January 2011

  • Sumida, Kenji; Brown, Craig M.; Herm, Zoey R.
  • Chemical Communications, Vol. 47, Issue 4, p. 1157-1159
  • DOI: 10.1039/C0CC03453C

Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design
journal, January 2015

  • Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang
  • Chemistry of Materials, Vol. 27, Issue 3, p. 668-678
  • DOI: 10.1021/cm502760q

Carbon-hydrogen and hydrogen-hydrogen activation in transition metal complexes and on surfaces
journal, April 1984

  • Saillard, Jean Yves; Hoffmann, Roald
  • Journal of the American Chemical Society, Vol. 106, Issue 7
  • DOI: 10.1021/ja00319a020

Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers
journal, April 2011


Ni/MIL-120: An efficient metal–organic framework catalyst for hydrogenation of benzene to cyclohexane
journal, May 2013


Advances on biomass pretreatment using ionic liquids: An overview
journal, January 2011

  • Tadesse, Haregewine; Luque, Rafael
  • Energy & Environmental Science, Vol. 4, Issue 10, p. 3913-3929
  • DOI: 10.1039/c0ee00667j

Works referencing / citing this record:

3D Enantiomorphic Mg‐Based Metal–Organic Frameworks as Chemical Sensor of Nitrobenzene and Efficient Catalyst for CO 2 Cycloaddition
journal, April 2019

  • Xue, Yun‐Shan; Cheng, Weiwei; Cao, Jia‐Peng
  • Chemistry – An Asian Journal, Vol. 14, Issue 11
  • DOI: 10.1002/asia.201900147

Incorporation of CuO NPs into modified UiO-66-NH 2 metal–organic frameworks (MOFs) with melamine for catalytic C–O coupling in the Ullmann condensation
journal, January 2017

  • Sadeghi, Samira; Jafarzadeh, Mohammad; Reza Abbasi, Amir
  • New Journal of Chemistry, Vol. 41, Issue 20
  • DOI: 10.1039/c7nj02114c

Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase
journal, April 2018


Design Rules for Metal‐Organic Framework Stability in High‐Pressure Hydrogen Environments
journal, March 2019


Catalysis of photooxidation reactions through transformation between Cu 2+ and Cu + in TiO 2 –Cu–MOF composites
journal, January 2018

  • Chen, Chunjun; Wu, Tianbin; Yang, Dexin
  • Chemical Communications, Vol. 54, Issue 47
  • DOI: 10.1039/c8cc03505a

Aerobic Oxidation of Benzylic Hydrocarbons by Iron‐Based Metal Organic Framework as Solid Heterogeneous Catalyst
journal, November 2018

  • Nagarjun, Nagarathinam; Dhakshinamoorthy, Amarajothi
  • ChemistrySelect, Vol. 3, Issue 43
  • DOI: 10.1002/slct.201802672

Synthesis of fluorescent MOFs: live-cell imaging and sensing of a herbicide
journal, January 2020

  • Mohanty, Aurobinda; Singh, Udai P.; Butcher, R. J.
  • CrystEngComm, Vol. 22, Issue 26
  • DOI: 10.1039/d0ce00490a

Exploring the multifunctionality in metal–organic framework materials: how do the stilbenedicarboxylate and imidazolyl ligands tune the characteristics of coordination polymers?
journal, January 2018

  • Barsukova, Marina O.; Sapchenko, Sergey A.; Kovalenko, Konstantin A.
  • New Journal of Chemistry, Vol. 42, Issue 8
  • DOI: 10.1039/c8nj00494c

Stimuli-Responsive DNA-Functionalized Metal-Organic Frameworks (MOFs)
journal, December 2016

  • Kahn, Jason S.; Freage, Lina; Enkin, Natalie
  • Advanced Materials, Vol. 29, Issue 6
  • DOI: 10.1002/adma.201602782

Size-dependent catalytic performance of ruthenium nanoparticles in the hydrogenolysis of a β-O-4 lignin model compound
journal, January 2018

  • Dong, Lin; Yin, Li-Li; Xia, Qineng
  • Catalysis Science & Technology, Vol. 8, Issue 3
  • DOI: 10.1039/c7cy02014g

Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction
journal, December 2019

  • Kidanemariam, Alemayehu; Lee, Jiwon; Park, Juhyun
  • Polymers, Vol. 11, Issue 12
  • DOI: 10.3390/polym11122090

ATP-Responsive Aptamer-Based Metal-Organic Framework Nanoparticles (NMOFs) for the Controlled Release of Loads and Drugs
journal, July 2017

  • Chen, Wei-Hai; Yu, Xu; Liao, Wei-Ching
  • Advanced Functional Materials, Vol. 27, Issue 37
  • DOI: 10.1002/adfm.201702102

Enzyme-Driven Release of Loads from Nucleic Acid-Capped Metal-Organic Framework Nanoparticles
journal, December 2018

  • Chen, Wei-Hai; Luo, Guo-Feng; Sohn, Yang Sung
  • Advanced Functional Materials, Vol. 29, Issue 5
  • DOI: 10.1002/adfm.201805341

Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models
journal, March 2018

  • Zeng, Huiying; Cao, Dawei; Qiu, Zihang
  • Angewandte Chemie International Edition, Vol. 57, Issue 14
  • DOI: 10.1002/anie.201712211

Biocatalytic cascades driven by enzymes encapsulated in metal–organic framework nanoparticles
journal, August 2018

  • Chen, Wei-Hai; Vázquez-González, Margarita; Zoabi, Amani
  • Nature Catalysis, Vol. 1, Issue 9
  • DOI: 10.1038/s41929-018-0117-2

Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models
journal, March 2018


Four coordination polymers derived from a one-pot reaction and their controlled synthesis
journal, January 2016

  • Yan, Wei; Hao, Han; Zheng, Hegen
  • Dalton Transactions, Vol. 45, Issue 15
  • DOI: 10.1039/c6dt00349d

Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase
journal, June 2018


Nanoparticle/Metal–Organic Framework Composites for Catalytic Applications: Current Status and Perspective
journal, November 2017


Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction
journal, December 2019

  • Kidanemariam, Alemayehu; Lee, Jiwon; Park, Juhyun
  • Polymers, Vol. 11, Issue 12
  • DOI: 10.3390/polym11122090