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 04:00:00 UTC 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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Sandia National Laboratories (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, Journal Name: ACS Catalysis Journal Issue: 1 Vol. 6; ISSN 2155-5435

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (30)

Hydrogenolysis Goes Bio: From Carbohydrates and Sugar Alcohols to Platform Chemicals Ruppert, Agnieszka M.; Weinberg, Kamil; Palkovits, Regina Angewandte Chemie International Edition, Vol. 51, Issue 11, p. 2564-2601 https://doi.org/10.1002/anie.201105125	journal	February 2012
Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin Wang, Xingyu; Rinaldi, Roberto ChemSusChem, Vol. 5, Issue 8, p. 1455-1466 https://doi.org/10.1002/cssc.201200040	journal	April 2012
Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions Meilikhov, Mikhail; Yusenko, Kirill; Esken, Daniel European Journal of Inorganic Chemistry, Vol. 2010, Issue 24, p. 3701-3714 https://doi.org/10.1002/ejic.201000473	journal	July 2010
Ni/MIL-120: An efficient metal–organic framework catalyst for hydrogenation of benzene to cyclohexane Wan, Ye; Chen, Chao; Xiao, Weiming Microporous and Mesoporous Materials, Vol. 171, p. 9-13 https://doi.org/10.1016/j.micromeso.2013.01.005	journal	May 2013
Porous Metal–Organic Frameworks for Heterogeneous Biomimetic Catalysis Zhao, Min; Ou, Sha; Wu, Chuan-De Accounts of Chemical Research, Vol. 47, Issue 4, p. 1199-1207 https://doi.org/10.1021/ar400265x	journal	February 2014
Catalytic Conversion of Nonfood Woody Biomass Solids to Organic Liquids Barta, Katalin; Ford, Peter C. Accounts of Chemical Research, Vol. 47, Issue 5, p. 1503-1512 https://doi.org/10.1021/ar4002894	journal	April 2014
Small-Molecule Adsorption in Open-Site Metal–Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design Lee, Kyuho; Howe, Joshua D.; Lin, Li-Chiang Chemistry of Materials, Vol. 27, Issue 3, p. 668-678 https://doi.org/10.1021/cm502760q	journal	January 2015
Asymmetric Hydrogenation of Heteroarenes and Arenes Wang, Duo-Sheng; Chen, Qing-An; Lu, Sheng-Mei Chemical Reviews, Vol. 112, Issue 4, p. 2557-2590 https://doi.org/10.1021/cr200328h	journal	November 2011
Advances in Coal Gasification, Hydrogenation, and Gas Treating for the Production of Chemicals and Fuels Higman, Christopher; Tam, Samuel Chemical Reviews, Vol. 114, Issue 3, p. 1673-1708 https://doi.org/10.1021/cr400202m	journal	October 2013
Water Stability and Adsorption in Metal–Organic Frameworks Burtch, Nicholas C.; Jasuja, Himanshu; Walton, Krista S. Chemical Reviews, Vol. 114, Issue 20, p. 10575-10612 https://doi.org/10.1021/cr5002589	journal	September 2014
Engineering Metal Organic Frameworks for Heterogeneous Catalysis Corma, A.; García, H.; Llabrés i Xamena, F. X. Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655 https://doi.org/10.1021/cr9003924	journal	August 2010
Metal Organic Framework Catalysis: Quo vadis ? Gascon, Jorge; Corma, Avelino; Kapteijn, Freek ACS Catalysis, Vol. 4, Issue 2, p. 361-378 https://doi.org/10.1021/cs400959k	journal	December 2013
Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation Guo, Zhiyong; Xiao, Chaoxian; Maligal-Ganesh, Raghu V. ACS Catalysis, Vol. 4, Issue 5, p. 1340-1348 https://doi.org/10.1021/cs400982n	journal	April 2014
Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals Wang, Lisa J.; Deng, Hexiang; Furukawa, Hiroyasu Inorganic Chemistry, Vol. 53, Issue 12, p. 5881-5883 https://doi.org/10.1021/ic500434a	journal	May 2014
Carbon-hydrogen and hydrogen-hydrogen activation in transition metal complexes and on surfaces Saillard, Jean Yves; Hoffmann, Roald Journal of the American Chemical Society, Vol. 106, Issue 7 https://doi.org/10.1021/ja00319a020	journal	April 1984
A Heterogeneous Nickel Catalyst for the Hydrogenolysis of Aryl Ethers without Arene Hydrogenation Sergeev, Alexey G.; Webb, Jonathan D.; Hartwig, John F. Journal of the American Chemical Society, Vol. 134, Issue 50, p. 20226-20229 https://doi.org/10.1021/ja3085912	journal	December 2012
Titanium Nitride-Nickel Nanocomposite as Heterogeneous Catalyst for the Hydrogenolysis of Aryl Ethers Molinari, Valerio; Giordano, Cristina; Antonietti, Markus Journal of the American Chemical Society, Vol. 136, Issue 5, p. 1758-1761 https://doi.org/10.1021/ja4119412	journal	January 2014
Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores Caskey, Stephen R.; Wong-Foy, Antek G.; Matzger, Adam J. Journal of the American Chemical Society, Vol. 130, Issue 33, p. 10870-10871 https://doi.org/10.1021/ja8036096	journal	August 2008
Noble Gas Adsorption in Metal–Organic Frameworks Containing Open Metal Sites Perry, John J.; Teich-McGoldrick, Stephanie L.; Meek, Scott T. The Journal of Physical Chemistry C, Vol. 118, Issue 22, p. 11685-11698 https://doi.org/10.1021/jp501495f	journal	May 2014
Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal–Organic Frameworks Aijaz, Arshad; Xu, Qiang The Journal of Physical Chemistry Letters, Vol. 5, Issue 8, p. 1400-1411 https://doi.org/10.1021/jz5004044	journal	March 2014
Reversible Hydrogen Storage by NaAlH ₄ Confined within a Titanium-Functionalized MOF-74(Mg) Nanoreactor Stavila, Vitalie; Bhakta, Raghunandan K.; Alam, Todd M. ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn304514c	journal	October 2012
Hydrogen storage properties and neutron scattering studies of Mg₂(dobdc)—a metal–organic framework with open Mg²⁺ adsorption sites Sumida, Kenji; Brown, Craig M.; Herm, Zoey R. Chemical Communications, Vol. 47, Issue 4, p. 1157-1159 https://doi.org/10.1039/C0CC03453C	journal	January 2011
Applications of metal–organic frameworks in heterogeneous supramolecular catalysis Liu, Jiewei; Chen, Lianfen; Cui, Hao Chemical Society Reviews, Vol. 43, Issue 16, p. 6011-6061 https://doi.org/10.1039/C4CS00094C	journal	January 2014
Catalytic nickel nanoparticles embedded in a mesoporous metal–organic framework Park, Young Kwan; Choi, Sang Beom; Nam, Hye Jin Chemical Communications, Vol. 46, Issue 18, p. 3086-3088 https://doi.org/10.1039/c000775g	journal	January 2010
Advances on biomass pretreatment using ionic liquids: An overview Tadesse, Haregewine; Luque, Rafael Energy & Environmental Science, Vol. 4, Issue 10, p. 3913-3929 https://doi.org/10.1039/c0ee00667j	journal	January 2011
High thermal and chemical stability in pyrazolate-bridged metal–organic frameworks with exposed metal sites Colombo, Valentina; Galli, Simona; Choi, Hye Jin Chemical Science, Vol. 2, Issue 7, p. 1311-1319 https://doi.org/10.1039/c1sc00136a	journal	January 2011
Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers Sergeev, A. G.; Hartwig, J. F. Science, Vol. 332, Issue 6028, p. 439-443 https://doi.org/10.1126/science.1200437	journal	April 2011
Large-Pore Apertures in a Series of Metal-Organic Frameworks Deng, H.; Grunder, S.; Cordova, K. E. Science, Vol. 336, Issue 6084, p. 1018-1023 https://doi.org/10.1126/science.1220131	journal	May 2012
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
Bio-inspired MOF-based Catalysts for Lignin Valorization Allendorf, Mark D.; Stavila, Vitalie; Ramakrishnan, Parthasarathi https://doi.org/10.2172/1159323	report	September 2014

Cited By (24)

Nanoparticle/Metal–Organic Framework Composites for Catalytic Applications: Current Status and Perspective Xiang, Wenlong; Zhang, Yueping; Lin, Hongfei Molecules, Vol. 22, Issue 12 https://doi.org/10.3390/molecules22122103	journal	November 2017
Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction Kidanemariam, Alemayehu; Lee, Jiwon; Park, Juhyun Polymers, Vol. 11, Issue 12 https://doi.org/10.3390/polym11122090	journal	December 2019
ATP-Responsive Aptamer-Based Metal-Organic Framework Nanoparticles (NMOFs) for the Controlled Release of Loads and Drugs Chen, Wei-Hai; Yu, Xu; Liao, Wei-Ching Advanced Functional Materials, Vol. 27, Issue 37 https://doi.org/10.1002/adfm.201702102	journal	July 2017
Enzyme-Driven Release of Loads from Nucleic Acid-Capped Metal-Organic Framework Nanoparticles Chen, Wei-Hai; Luo, Guo-Feng; Sohn, Yang Sung Advanced Functional Materials, Vol. 29, Issue 5 https://doi.org/10.1002/adfm.201805341	journal	December 2018
Stimuli-Responsive DNA-Functionalized Metal-Organic Frameworks (MOFs) Kahn, Jason S.; Freage, Lina; Enkin, Natalie Advanced Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adma.201602782	journal	December 2016
Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models Zeng, Huiying; Cao, Dawei; Qiu, Zihang Angewandte Chemie, Vol. 130, Issue 14 https://doi.org/10.1002/ange.201712211	journal	March 2018
Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models Zeng, Huiying; Cao, Dawei; Qiu, Zihang Angewandte Chemie International Edition, Vol. 57, Issue 14 https://doi.org/10.1002/anie.201712211	journal	March 2018
3D Enantiomorphic Mg‐Based Metal–Organic Frameworks as Chemical Sensor of Nitrobenzene and Efficient Catalyst for CO 2 Cycloaddition Xue, Yun‐Shan; Cheng, Weiwei; Cao, Jia‐Peng Chemistry – An Asian Journal, Vol. 14, Issue 11 https://doi.org/10.1002/asia.201900147	journal	April 2019
Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase Chen, Hao; He, Yulian; Pfefferle, Lisa D. ChemCatChem, Vol. 10, Issue 12 https://doi.org/10.1002/cctc.201800211	journal	April 2018
Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase Chen, Hao; He, Yulian; Pfefferle, Lisa D. ChemCatChem, Vol. 10, Issue 12 https://doi.org/10.1002/cctc.201800907	journal	June 2018
Design Rules for Metal‐Organic Framework Stability in High‐Pressure Hydrogen Environments Wang, Timothy C.; White, James L.; Bie, Binglin ChemPhysChem, Vol. 20, Issue 10 https://doi.org/10.1002/cphc.201801190	journal	March 2019
Aerobic Oxidation of Benzylic Hydrocarbons by Iron‐Based Metal Organic Framework as Solid Heterogeneous Catalyst Nagarjun, Nagarathinam; Dhakshinamoorthy, Amarajothi ChemistrySelect, Vol. 3, Issue 43 https://doi.org/10.1002/slct.201802672	journal	November 2018
Biocatalytic cascades driven by enzymes encapsulated in metal–organic framework nanoparticles Chen, Wei-Hai; Vázquez-González, Margarita; Zoabi, Amani Nature Catalysis, Vol. 1, Issue 9 https://doi.org/10.1038/s41929-018-0117-2	journal	August 2018
MOF catalysts in biomass upgrading towards value-added fine chemicals Herbst, Annika; Janiak, Christoph CrystEngComm, Vol. 19, Issue 29 https://doi.org/10.1039/c6ce01782g	journal	January 2017
Four coordination polymers derived from a one-pot reaction and their controlled synthesis Yan, Wei; Hao, Han; Zheng, Hegen Dalton Transactions, Vol. 45, Issue 15 https://doi.org/10.1039/c6dt00349d	journal	January 2016
An efficient approach for enhancing the catalytic activity of Ni-MOF-74 via a relay catalyst system for the selective oxidation of benzylic C–H bonds under mild conditions Guo, Changyan; Zhang, Yonghong; Zhang, Yi Chemical Communications, Vol. 54, Issue 30 https://doi.org/10.1039/c7cc09602j	journal	January 2018
Size-dependent catalytic performance of ruthenium nanoparticles in the hydrogenolysis of a β-O-4 lignin model compound Dong, Lin; Yin, Li-Li; Xia, Qineng Catalysis Science & Technology, Vol. 8, Issue 3 https://doi.org/10.1039/c7cy02014g	journal	January 2018
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 Sadeghi, Samira; Jafarzadeh, Mohammad; Reza Abbasi, Amir New Journal of Chemistry, Vol. 41, Issue 20 https://doi.org/10.1039/c7nj02114c	journal	January 2017
Catalysis of photooxidation reactions through transformation between Cu ²⁺ and Cu ⁺ in TiO ₂ –Cu–MOF composites Chen, Chunjun; Wu, Tianbin; Yang, Dexin Chemical Communications, Vol. 54, Issue 47 https://doi.org/10.1039/c8cc03505a	journal	January 2018
Covalent triazine framework catalytic oxidative cleavage of lignin models and organosolv lignin Zhao, Li; Shi, Song; Liu, Meng Green Chemistry, Vol. 20, Issue 6 https://doi.org/10.1039/c8gc00268a	journal	January 2018
Exploring the multifunctionality in metal–organic framework materials: how do the stilbenedicarboxylate and imidazolyl ligands tune the characteristics of coordination polymers? Barsukova, Marina O.; Sapchenko, Sergey A.; Kovalenko, Konstantin A. New Journal of Chemistry, Vol. 42, Issue 8 https://doi.org/10.1039/c8nj00494c	journal	January 2018
IRMOF-74( n )–Mg: a novel catalyst series for hydrogen activation and hydrogenolysis of C–O bonds Stavila, Vitalie; Foster, Michael E.; Brown, Jonathan W. Chemical Science, Vol. 10, Issue 42 https://doi.org/10.1039/c9sc01018a	journal	January 2019
Synthesis of fluorescent MOFs: live-cell imaging and sensing of a herbicide Mohanty, Aurobinda; Singh, Udai P.; Butcher, R. J. CrystEngComm, Vol. 22, Issue 26 https://doi.org/10.1039/d0ce00490a	journal	January 2020
Recent Innovation of Metal-Organic Frameworks for Carbon Dioxide Photocatalytic Reduction Kidanemariam, Alemayehu; Lee, Jiwon; Park, Juhyun Polymers, Vol. 11, Issue 12 https://doi.org/10.3390/polym11122090	journal	December 2019

Similar Records

The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C-O Bonds

Journal Article · Mon Jan 20 04:00:00 UTC 2020 · Angewandte Chemie International Edition · OSTI ID:1614997

Wang, Meng; Zhao, Yuntao; Mei, Donghai; +4 more

The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds

Journal Article · Thu Dec 12 04:00:00 UTC 2019 · Angewandte Chemie (International Edition) · OSTI ID:1605477

Wang, Meng; Zhao, Yuntao; Mei, Donghai; +4 more

The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds

Journal Article · Thu Dec 12 04:00:00 UTC 2019 · Angewandte Chemie · OSTI ID:1579369

Wang, Meng; Zhao, Yuntao; Mei, Donghai; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C−O bond cleavage
aromatic ethers
catalysis
hydrogenolysis
metal−organic frameworks

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

Citation Formats

References (30)

Cited By (24)

Similar Records

Related Subjects