Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol

Suh, Bong Lim; Kim, Jihan

doi:10.1021/acs.jpcc.8b07857

Title: Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol

Abstract

We report that efficient conversion of ethane into valuable materials is important with the availability of new natural gas resources. Recently, metal–organic frameworks (MOFs) with open iron sites (i.e., Fe_0.1Mg_1.9-MOF-74) have been shown to be promising material for catalyzing ethane to ethanol. In this computational study, various size-matching ligands are inserted into the Fe_0.1Mg_1.9-MOF-74 structure to further optimize this reaction. Our density functional theory calculations show that the presence of ligands enhances the binding affinity of the oxygen atoms of N2O to the iron atoms in the framework, thereby leading to an improvement in the oxidizing process. Furthermore, the reaction pathways for the new structures show reduced enthalpy barrier in the rate-determining step in the oxidation of ethane reaction cycle compared to the original Fe_0.1Mg_1.9-MOF-74. In conclusion, these findings provide ways in which the performance of the Fe_0.1Mg_1.9-MOF-74 can be optimized for next-generation catalysts.

Authors:

^[1]; Kim, Jihan ^[1]

Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)

Publication Date:: Mon Sep 24 00:00:00 EDT 2018

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1543654

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 122; Journal Issue: 40; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Suh, Bong Lim, and Kim, Jihan. Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcc.8b07857.

Copy to clipboard


                    Suh, Bong Lim, & Kim, Jihan. Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol.  United States.  https://doi.org/10.1021/acs.jpcc.8b07857

Copy to clipboard


                    Suh, Bong Lim, and Kim, Jihan. Mon .  
"Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol".  United States.  https://doi.org/10.1021/acs.jpcc.8b07857.  https://www.osti.gov/servlets/purl/1543654.

Copy to clipboard


                    
@article{osti_1543654,

  title        = {Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol},

  author       = {Suh, Bong Lim and Kim, Jihan},

  abstractNote = {We report that efficient conversion of ethane into valuable materials is important with the availability of new natural gas resources. Recently, metal–organic frameworks (MOFs) with open iron sites (i.e., Fe0.1Mg1.9-MOF-74) have been shown to be promising material for catalyzing ethane to ethanol. In this computational study, various size-matching ligands are inserted into the Fe0.1Mg1.9-MOF-74 structure to further optimize this reaction. Our density functional theory calculations show that the presence of ligands enhances the binding affinity of the oxygen atoms of N2O to the iron atoms in the framework, thereby leading to an improvement in the oxidizing process. Furthermore, the reaction pathways for the new structures show reduced enthalpy barrier in the rate-determining step in the oxidation of ethane reaction cycle compared to the original Fe0.1Mg1.9-MOF-74. In conclusion, these findings provide ways in which the performance of the Fe0.1Mg1.9-MOF-74 can be optimized for next-generation catalysts.},

  doi          = {10.1021/acs.jpcc.8b07857},

  journal      = {Journal of Physical Chemistry. C},

  number       = 40,

  volume       = 122,

  place        = {United States},

  year         = {Mon Sep 24 00:00:00 EDT 2018},

  month        = {Mon Sep 24 00:00:00 EDT 2018}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jpcc.8b07857

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 17 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Natural gas origin, composition, and processing: A review
journal, August 2016

Faramawy, S.; Zaki, T.; Sakr, A. A. -E.
Journal of Natural Gas Science and Engineering, Vol. 34
DOI: 10.1016/j.jngse.2016.06.030

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century
journal, December 2000

Lunsford, Jack H.
Catalysis Today, Vol. 63, Issue 2-4, p. 165-174
DOI: 10.1016/S0920-5861(00)00456-9

Progress in the direct catalytic conversion of methane to fuels and chemicals
journal, July 2016

Karakaya, Canan; Kee, Robert J.
Progress in Energy and Combustion Science, Vol. 55
DOI: 10.1016/j.pecs.2016.04.003

Unconventional Chemistry for Unconventional Natural Gas
journal, October 2012

McFarland, E.
Science, Vol. 338, Issue 6105
DOI: 10.1126/science.1226840

Direct conversion technologies of methane to methanol: An overview
journal, November 2016

Zakaria, Z.; Kamarudin, S. K.
Renewable and Sustainable Energy Reviews, Vol. 65
DOI: 10.1016/j.rser.2016.05.082

Selective Methane Oxidation Catalyzed by Platinum Salts in Oleum at Turnover Frequencies of Large-Scale Industrial Processes
journal, September 2016

Zimmermann, Tobias; Soorholtz, Mario; Bilke, Marius
Journal of the American Chemical Society, Vol. 138, Issue 38
DOI: 10.1021/jacs.6b05167

Solid Catalysts for the Selective Low-Temperature Oxidation of Methane to Methanol
journal, September 2009

Palkovits, Regina; Antonietti, Markus; Kuhn, Pierre
Angewandte Chemie International Edition, Vol. 48, Issue 37
DOI: 10.1002/anie.200902009

Elucidation and Evolution of the Active Component within Cu/Fe/ZSM-5 for Catalytic Methane Oxidation: From Synthesis to Catalysis
journal, February 2013

Hammond, Ceri; Dimitratos, Nikolaos; Jenkins, Robert L.
ACS Catalysis, Vol. 3, Issue 4
DOI: 10.1021/cs3007999

Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5
journal, April 2012

Hammond, Ceri; Forde, Michael M.; Ab Rahim, Mohd Hasbi
Angewandte Chemie International Edition, Vol. 51, Issue 21
DOI: 10.1002/anie.201108706

Iron complexes in zeolites as a new model of methane monooxygenase
journal, July 1997

Panov, G. I.; Sobolev, V. I.; Dubkov, K. A.
Reaction Kinetics and Catalysis Letters, Vol. 61, Issue 2
DOI: 10.1007/BF02478380

Monocopper Active Site for Partial Methane Oxidation in Cu-Exchanged 8MR Zeolites
journal, September 2016

Kulkarni, Ambarish R.; Zhao, Zhi-Jian; Siahrostami, Samira
ACS Catalysis, Vol. 6, Issue 10
DOI: 10.1021/acscatal.6b01895

Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites
journal, May 2014

Xiao, Dianne J.; Bloch, Eric D.; Mason, Jarad A.
Nature Chemistry, Vol. 6, Issue 7
DOI: 10.1038/nchem.1956

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)–Oxo Sites in Magnesium-Diluted Fe ₂ (dobdc)
journal, April 2015

Verma, Pragya; Vogiatzis, Konstantinos D.; Planas, Nora
Journal of the American Chemical Society, Vol. 137, Issue 17
DOI: 10.1021/jacs.5b00382

Multiscale Model for a Metal–Organic Framework: High-Spin Rebound Mechanism in the Reaction of the Oxoiron(IV) Species of Fe-MOF-74
journal, April 2015

Hirao, Hajime; Ng, Wilson Kwok Hung; Moeljadi, Adhitya Mangala Putra
ACS Catalysis, Vol. 5, Issue 6
DOI: 10.1021/acscatal.5b00475

Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study
journal, April 2017

Liao, Peilin; Getman, Rachel B.; Snurr, Randall Q.
ACS Applied Materials & Interfaces, Vol. 9, Issue 39
DOI: 10.1021/acsami.7b02195

Preparation, Clathration Ability, and Catalysis of a Two-Dimensional Square Network Material Composed of Cadmium(II) and 4,4'-Bipyridine
journal, February 1994

Fujita, Makoto; Kwon, Yoon Jung; Washizu, Satoru
Journal of the American Chemical Society, Vol. 116, Issue 3
DOI: 10.1021/ja00082a055

High activity of iron containing metal–organic-framework in acylation of p-xylene with benzoyl chloride
journal, January 2012

Kurfiřtová, Lenka; Seo, You-Kyong; Hwang, Young Kyu
Catalysis Today, Vol. 179, Issue 1
DOI: 10.1016/j.cattod.2011.08.001

MOF-5 as an efficient heterogeneous catalyst for Friedel–Crafts alkylation reactions
journal, July 2010

Phan, Nam T. S.; Le, Ky K. A.; Phan, Tuan D.
Applied Catalysis A: General, Vol. 382, Issue 2
DOI: 10.1016/j.apcata.2010.04.053

Cooperative Guest Inclusion by a Zeolite Analogue Coordination Polymer. Sorption Behavior with Gases and Amine and Group 1 Metal Salts
journal, January 2001

Tabares, Leandro C.; Navarro, Jorge A. R.; Salas, Juan M.
Journal of the American Chemical Society, Vol. 123, Issue 3
DOI: 10.1021/ja002624a

Size-Matching Ligand Insertion in MOF-74 for Enhanced CO ₂ Capture under Humid Conditions
journal, October 2017

Suh, Bong Lim; Lee, Sangwon; Kim, Jihan
The Journal of Physical Chemistry C, Vol. 121, Issue 44
DOI: 10.1021/acs.jpcc.7b08239

Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake
journal, January 2015

Zhao, Xiang; Bu, Xianhui; Zhai, Quan-Guo
Journal of the American Chemical Society, Vol. 137, Issue 4
DOI: 10.1021/ja512137t

Projector augmented-wave method
journal, December 1994

Blöchl, P. E.
Physical Review B, Vol. 50, Issue 24, p. 17953-17979
DOI: 10.1103/PhysRevB.50.17953

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007

Zhao, Yan; Truhlar, Donald G.
Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
DOI: 10.1007/s00214-007-0310-x

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Weigend, Florian; Ahlrichs, Reinhart
Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
DOI: 10.1039/b508541a

Accurate Coulomb-fitting basis sets for H to Rn
journal, January 2006

Weigend, Florian
Physical Chemistry Chemical Physics, Vol. 8, Issue 9
DOI: 10.1039/b515623h

Works referencing / citing this record:

Rational modifications of PCN-700 to induce electrical conductivity: a computational study
journal, January 2020

Chong, Sanggyu; Kim, Jihan
Dalton Transactions, Vol. 49, Issue 1
DOI: 10.1039/c9dt03865e

Similar Records in DOE PAGES and OSTI.GOV collections:

Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study

Journal Article Liao, Peilin ; Getman, Rachel B. ; Snurr, Randall Q. - ACS Applied Materials and Interfaces

Activation of the C-H bonds in ethane to form ethanol is a highly desirable, yet challenging, reaction. Metal- organic frameworks (MOFs) with open Fe sites are promising candidates for catalyzing this reaction. One advantage of MOFs is their modular construction from inorganic nodes and organic linkers, allowing for flexible design and detailed control of properties. In this work, we studied a series of single-metal atom Fe model systems with ligands that are commonly used as MOF linkers and tried to understand how one can design an optimal Fe catalyst. We found linear relationships between the binding enthalpy of oxygen tomore »« less
Cited by 42
https://doi.org/10.1021/acsami.7b02195
Oxidation of ethane to ethanol by N₂O in a metal–organic framework with coordinatively unsaturated iron(II) sites [Oxidation of ethane to ethanol by nitrous oxide in a metal–organic framework with coordinatively unsaturated iron(II) sites]

Journal Article Xiao, Dianne J. ; Bloch, Eric D. ; Mason, Jarad A. ; ... - Nature Chemistry

Enzymatic heme and non-heme high-valent iron-oxo species are known to activate strong C–H bonds with relative ease, yet duplicating this reactivity in a synthetic system remains a formidable challenge. While the instability of the terminal iron-oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)-oxo compounds. In particular, while nature’s non-heme iron(IV)-oxos possess high-spin S = 2 ground states, this electronic configuration has proven difficult to achieve in a molecular species. These challenges may be mitigated within metal-organic frameworks featuring site-isolated iron centers in a constrained, weak-field ligand environment. Asmore »« less
Cited by 341
https://doi.org/10.1038/nchem.1956

Full Text Available
Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)–Oxo Sites in Magnesium-Diluted Fe₂(dobdc)

Journal Article Verma, Pragya ; Vogiatzis, Konstantinos D. ; Planas, Nora ; ... - Journal of the American Chemical Society

The catalytic properties of the metal–organic framework Fe₂(dobdc), containing open Fe(II) sites, include hydroxylation of phenol by pure Fe₂(dobdc) and hydroxylation of ethane by its magnesium-diluted analogue, Fe_0.1Mg_1.9(dobdc). In earlier work, the latter reaction was proposed to occur through a redox mechanism involving the generation of an iron(IV)–oxo species, which is an intermediate that is also observed or postulated (depending on the case) in some heme and non-heme enzymes and their model complexes. In the present work, we present a detailed mechanism by which the catalytic material, Fe_0.1Mg_1.9(dobdc), activates the strong C–H bonds of ethane. Kohn–Sham density functional and multireferencemore »« less
https://doi.org/10.1021/jacs.5b00382

Full Text Available
Oxidation of ethane to ethanol by N₂O in a metal-organic framework with coordinatively unsaturated iron(II) sites

Journal Article Xiao, Dianne J. ; Bloch, Eric D. ; Mason, Jarad A. ; ... - Nat. Chem.

Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we showmore »« less
https://doi.org/10.1038/nchem.1956
Thermodynamics Drives the Stability of the MOF-74 Family in Water

Journal Article Voskanyan, Albert A. ; Goncharov, Vitaliy G. ; Novendra, Novendra ; ... - ACS Omega

The stability of functional materials in water-containing environments is critical for their industrial applications. A wide variety of metal–organic frameworks (MOFs) synthesized in the past decade have strikingly different apparent stabilities in contact with liquid or gaseous H₂O, ranging from rapid hydrolysis to persistence over days to months. Here, we show using newly determined thermochemical data obtained by high-temperature drop combustion calorimetry that these differences are thermodynamically driven rather than primarily kinetically controlled. The formation reaction of a MOF from metal oxide (MO) and a linker generally liberates water by the reaction MO + linker = MOF + H₂O. Newlymore »« less
Cited by 22
https://doi.org/10.1021/acsomega.0c01189

Similar Records

Title: Ligand Insertion in MOF-74 as Effective Design for Oxidation of Ethane to Ethanol

Abstract

Citation Formats

Natural gas origin, composition, and processing: A review journal, August 2016

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century journal, December 2000

Progress in the direct catalytic conversion of methane to fuels and chemicals journal, July 2016

Unconventional Chemistry for Unconventional Natural Gas journal, October 2012

Direct conversion technologies of methane to methanol: An overview journal, November 2016

Selective Methane Oxidation Catalyzed by Platinum Salts in Oleum at Turnover Frequencies of Large-Scale Industrial Processes journal, September 2016

Solid Catalysts for the Selective Low-Temperature Oxidation of Methane to Methanol journal, September 2009

Elucidation and Evolution of the Active Component within Cu/Fe/ZSM-5 for Catalytic Methane Oxidation: From Synthesis to Catalysis journal, February 2013

Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5 journal, April 2012

Iron complexes in zeolites as a new model of methane monooxygenase journal, July 1997

Monocopper Active Site for Partial Methane Oxidation in Cu-Exchanged 8MR Zeolites journal, September 2016

Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites journal, May 2014

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)–Oxo Sites in Magnesium-Diluted Fe 2 (dobdc) journal, April 2015

Multiscale Model for a Metal–Organic Framework: High-Spin Rebound Mechanism in the Reaction of the Oxoiron(IV) Species of Fe-MOF-74 journal, April 2015

Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study journal, April 2017

Preparation, Clathration Ability, and Catalysis of a Two-Dimensional Square Network Material Composed of Cadmium(II) and 4,4'-Bipyridine journal, February 1994

High activity of iron containing metal–organic-framework in acylation of p-xylene with benzoyl chloride journal, January 2012

MOF-5 as an efficient heterogeneous catalyst for Friedel–Crafts alkylation reactions journal, July 2010

Cooperative Guest Inclusion by a Zeolite Analogue Coordination Polymer. Sorption Behavior with Gases and Amine and Group 1 Metal Salts journal, January 2001

Size-Matching Ligand Insertion in MOF-74 for Enhanced CO 2 Capture under Humid Conditions journal, October 2017

Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake journal, January 2015

Projector augmented-wave method journal, December 1994

Generalized Gradient Approximation Made Simple journal, October 1996

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal, July 2007

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal, January 2005

Accurate Coulomb-fitting basis sets for H to Rn journal, January 2006

Rational modifications of PCN-700 to induce electrical conductivity: a computational study journal, January 2020

Natural gas origin, composition, and processing: A review
journal, August 2016

Catalytic conversion of methane to more useful chemicals and fuels: a challenge for the 21st century
journal, December 2000

Progress in the direct catalytic conversion of methane to fuels and chemicals
journal, July 2016

Unconventional Chemistry for Unconventional Natural Gas
journal, October 2012

Direct conversion technologies of methane to methanol: An overview
journal, November 2016

Selective Methane Oxidation Catalyzed by Platinum Salts in Oleum at Turnover Frequencies of Large-Scale Industrial Processes
journal, September 2016

Solid Catalysts for the Selective Low-Temperature Oxidation of Methane to Methanol
journal, September 2009

Elucidation and Evolution of the Active Component within Cu/Fe/ZSM-5 for Catalytic Methane Oxidation: From Synthesis to Catalysis
journal, February 2013

Direct Catalytic Conversion of Methane to Methanol in an Aqueous Medium by using Copper-Promoted Fe-ZSM-5
journal, April 2012

Iron complexes in zeolites as a new model of methane monooxygenase
journal, July 1997

Monocopper Active Site for Partial Methane Oxidation in Cu-Exchanged 8MR Zeolites
journal, September 2016

Oxidation of ethane to ethanol by N2O in a metal–organic framework with coordinatively unsaturated iron(II) sites
journal, May 2014

Mechanism of Oxidation of Ethane to Ethanol at Iron(IV)–Oxo Sites in Magnesium-Diluted Fe ₂ (dobdc)
journal, April 2015

Multiscale Model for a Metal–Organic Framework: High-Spin Rebound Mechanism in the Reaction of the Oxoiron(IV) Species of Fe-MOF-74
journal, April 2015

Optimizing Open Iron Sites in Metal–Organic Frameworks for Ethane Oxidation: A First-Principles Study
journal, April 2017

Preparation, Clathration Ability, and Catalysis of a Two-Dimensional Square Network Material Composed of Cadmium(II) and 4,4'-Bipyridine
journal, February 1994

High activity of iron containing metal–organic-framework in acylation of p-xylene with benzoyl chloride
journal, January 2012

MOF-5 as an efficient heterogeneous catalyst for Friedel–Crafts alkylation reactions
journal, July 2010

Cooperative Guest Inclusion by a Zeolite Analogue Coordination Polymer. Sorption Behavior with Gases and Amine and Group 1 Metal Salts
journal, January 2001

Size-Matching Ligand Insertion in MOF-74 for Enhanced CO ₂ Capture under Humid Conditions
journal, October 2017

Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake
journal, January 2015

Projector augmented-wave method
journal, December 1994

Generalized Gradient Approximation Made Simple
journal, October 1996

The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

Accurate Coulomb-fitting basis sets for H to Rn
journal, January 2006

Rational modifications of PCN-700 to induce electrical conductivity: a computational study
journal, January 2020