skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Cation-exchanged zeolites for the selective oxidation of methane to methanol

Abstract

Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metal cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites formore » this industrially relevant conversion.« less

Authors:
ORCiD logo [1];  [2];  [1];  [1]; ORCiD logo [3]
  1. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
  2. Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering; SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis ; Tianjin University, Collaborative Innovation Center of Chemical Science and Engineering (China). Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology
  3. Karlsruhe Institute of Technology (Germany). Institute of Catalysis Research and Technology and Institute for Chemical Technology and Polymer Chemistry
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1426493
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kulkarni, Ambarish R., Zhao, Zhi-Jian, Siahrostami, Samira, Nørskov, Jens K., and Studt, Felix. Cation-exchanged zeolites for the selective oxidation of methane to methanol. United States: N. p., 2017. Web. doi:10.1039/c7cy01229b.
Kulkarni, Ambarish R., Zhao, Zhi-Jian, Siahrostami, Samira, Nørskov, Jens K., & Studt, Felix. Cation-exchanged zeolites for the selective oxidation of methane to methanol. United States. doi:10.1039/c7cy01229b.
Kulkarni, Ambarish R., Zhao, Zhi-Jian, Siahrostami, Samira, Nørskov, Jens K., and Studt, Felix. Thu . "Cation-exchanged zeolites for the selective oxidation of methane to methanol". United States. doi:10.1039/c7cy01229b. https://www.osti.gov/servlets/purl/1426493.
@article{osti_1426493,
title = {Cation-exchanged zeolites for the selective oxidation of methane to methanol},
author = {Kulkarni, Ambarish R. and Zhao, Zhi-Jian and Siahrostami, Samira and Nørskov, Jens K. and Studt, Felix},
abstractNote = {Motivated by the increasing availability of cheap natural gas resources, considerable experimental and computational research efforts have focused on identifying selective catalysts for the direct conversion of methane to methanol. One promising class of catalysts are cation-exchanged zeolites, which have steadily increased in popularity over the past decade. Here, in this article, we first present a broad overview of this field from a conceptual perspective, and highlight the role of theory in developing a molecular-level understanding of the reaction. Next, by performing and analyzing a large database of density functional theory (DFT) calculations for a wide range of transition metal cations, zeolite topologies and active site motifs, we present a unifying picture of the methane activation process in terms of active site stability, C–H bond activation and methanol extraction. Based on the trade-offs of active site stability and reactivity, we propose a framework for identifying new, promising active site motifs in these systems. Further, we show that the high methanol selectivity arises due to the strong binding nature of the C–H activation products. Lastly, using the atomistic and mechanistic insight obtained from these analyses, we summarize the key challenges and future strategies for improving the performance of cation-exchanged zeolites for this industrially relevant conversion.},
doi = {10.1039/c7cy01229b},
journal = {Catalysis Science and Technology},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 22 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Selective Oxidation of Methane by the Bis(μ-oxo)dicopper Core Stabilized on ZSM-5 and Mordenite Zeolites
journal, February 2005

  • Groothaert, Marijke H.; Smeets, Pieter J.; Sels, Bert F.
  • Journal of the American Chemical Society, Vol. 127, Issue 5
  • DOI: 10.1021/ja047158u

Catalytic conversion of methane to methanol on Cu-SSZ-13 using N 2 O as oxidant
journal, January 2016

  • Ipek, B.; Lobo, R. F.
  • Chemical Communications, Vol. 52, Issue 91
  • DOI: 10.1039/C6CC07893A

Quantum mechanical calculations suggest that lytic polysaccharide monooxygenases use a copper-oxyl, oxygen-rebound mechanism
journal, December 2013

  • Kim, S.; Stahlberg, J.; Sandgren, M.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 1
  • DOI: 10.1073/pnas.1316609111

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature
journal, April 2016


Methane Activation by Selective Oxidation
journal, March 2016


General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides
journal, May 2017

  • Fung, Victor; Tao, Franklin Feng; Jiang, De-en
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
  • DOI: 10.1021/acs.jpclett.7b00861

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

Methane Activation on Zn 2+ -Exchanged ZSM-5 Zeolites. The Effect of Molecular Oxygen Addition
journal, October 2015

  • Gabrienko, Anton A.; Arzumanov, Sergei S.; Luzgin, Mikhail V.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 44
  • DOI: 10.1021/acs.jpcc.5b08759

Reactivity and Selectivity Descriptors for the Activation of C–H Bonds in Hydrocarbons and Oxygenates on Metal Oxides
journal, July 2016

  • Deshlahra, Prashant; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b04604

Formation of [Cu 2 O 2 ] 2+ and [Cu 2 O] 2+ toward C–H Bond Activation in Cu-SSZ-13 and Cu-SSZ-39
journal, May 2017


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

The Direct Catalytic Oxidation of Methane to Methanol-A Critical Assessment
journal, November 2017

  • Ravi, Manoj; Ranocchiari, Marco; van Bokhoven, Jeroen A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 52
  • DOI: 10.1002/anie.201702550

Advances in methane conversion processes
journal, May 2017


Metal dimer sites in ZSM-5 zeolite for methane-to-methanol conversion from first-principles kinetic modelling: is the [Cu–O–Cu] 2+ motif relevant for Ni, Co, Fe, Ag, and Au?
journal, January 2017

  • Arvidsson, Adam A.; Zhdanov, Vladimir P.; Carlsson, Per-Anders
  • Catalysis Science & Technology, Vol. 7, Issue 7
  • DOI: 10.1039/C6CY02521H

Catalytic and Mechanistic Insights of the Low-Temperature Selective Oxidation of Methane over Cu-Promoted Fe-ZSM-5
journal, November 2012

  • Hammond, Ceri; Jenkins, Robert L.; Dimitratos, Nikolaos
  • Chemistry - A European Journal, Vol. 18, Issue 49
  • DOI: 10.1002/chem.201202802

Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol
journal, June 2015

  • Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8546

Room temperature activation of methane over Zn modified H-ZSM-5 zeolites: Insight from solid-state NMR and theoretical calculations
journal, January 2012

  • Xu, Jun; Zheng, Anmin; Wang, Xiumei
  • Chemical Science, Vol. 3, Issue 10
  • DOI: 10.1039/c2sc20434g

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Development of Molecular and Solid Catalysts for the Direct Low-Temperature Oxidation of Methane to Methanol
journal, February 2010

  • Palkovits, Regina; von Malotki, Christian; Baumgarten, Martin
  • ChemSusChem, Vol. 3, Issue 2
  • DOI: 10.1002/cssc.200900123

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


Methane-to-Methanol Oxidation by the Hydrated Iron(IV) Oxo Species in Aqueous Solution:  A Combined DFT and Car−Parrinello Molecular Dynamics Study
journal, April 2004

  • Ensing, Bernd; Buda, Francesco; Gribnau, Michiel C. M.
  • Journal of the American Chemical Society, Vol. 126, Issue 13
  • DOI: 10.1021/ja038865a

Computationally Exploring Confinement Effects in the Methane-to-Methanol Conversion Over Iron-Oxo Centers in Zeolites
journal, November 2016

  • Göltl, Florian; Michel, Carine; Andrikopoulos, Prokopis C.
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b02640

Effect of Location and Distribution of Al Sites in ZSM-5 on the Formation of Cu-Oxo Clusters Active for Direct Conversion of Methane to Methanol
journal, August 2016

  • Markovits, Monica A. C.; Jentys, Andreas; Tromp, Moniek
  • Topics in Catalysis, Vol. 59, Issue 17-18
  • DOI: 10.1007/s11244-016-0676-x

Conversion of methane to methanol on copper-containing small-pore zeolites and zeotypes
journal, January 2015

  • Wulfers, M. J.; Teketel, S.; Ipek, B.
  • Chemical Communications, Vol. 51, Issue 21
  • DOI: 10.1039/C4CC09645B

Methane Activation by Heterogeneous Catalysis
journal, November 2014


Spectroscopy and Redox Chemistry of Copper in Mordenite
journal, January 2014

  • Vanelderen, Pieter; Vancauwenbergh, Julie; Tsai, Ming-Li
  • ChemPhysChem, Vol. 15, Issue 1
  • DOI: 10.1002/cphc.201300730

Kinetic isotope effects and mechanism of biomimetic oxidation of methane and benzene on FeZSM-5 zeolite
journal, August 1997


Cu-ZSM-5: A biomimetic inorganic model for methane oxidation
journal, December 2011


Direct Conversion of Methane to Methanol under Mild Conditions over Cu-Zeolites and beyond
journal, January 2017

  • Tomkins, Patrick; Ranocchiari, Marco; van Bokhoven, Jeroen A.
  • Accounts of Chemical Research, Vol. 50, Issue 2
  • DOI: 10.1021/acs.accounts.6b00534

Stability and reactivity of copper oxo-clusters in ZSM-5 zeolite for selective methane oxidation to methanol
journal, June 2016


Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative
journal, April 1998


Bis(μ-oxo) versus mono(μ-oxo)dicopper cores in a zeolite for converting methane to methanol: an in situ XAS and DFT investigation
journal, January 2015

  • Alayon, Evalyn Mae C.; Nachtegaal, Maarten; Bodi, Andras
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 12
  • DOI: 10.1039/C4CP03226H

Partial Oxidation of Methane to Methanol over Heterogeneous Catalyst Co/ZSM-5
journal, January 2015


Revisiting the nature of Cu sites in the activated Cu-SSZ-13 catalyst for SCR reaction
journal, January 2015

  • Borfecchia, E.; Lomachenko, K. A.; Giordanino, F.
  • Chemical Science, Vol. 6, Issue 1
  • DOI: 10.1039/C4SC02907K

Strategies for the Direct Catalytic Valorization of Methane Using Heterogeneous Catalysis: Challenges and Opportunities
journal, April 2016

  • Olivos-Suarez, Alma I.; Szécsényi, Àgnes; Hensen, Emiel J. M.
  • ACS Catalysis, Vol. 6, Issue 5
  • DOI: 10.1021/acscatal.6b00428

A [Cu 2 O] 2+ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol
journal, October 2009

  • Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 45
  • DOI: 10.1073/pnas.0910461106

Catalytic conversion of methane to methanol over Cu–mordenite
journal, January 2012

  • Alayon, Evalyn Mae; Nachtegaal, Maarten; Ranocchiari, Marco
  • Chem. Commun., Vol. 48, Issue 3
  • DOI: 10.1039/C1CC15840F

Oxygen Precursor to the Reactive Intermediate in Methanol Synthesis by Cu-ZSM-5
journal, October 2010

  • Smeets, Pieter J.; Hadt, Ryan G.; Woertink, Julia S.
  • Journal of the American Chemical Society, Vol. 132, Issue 42
  • DOI: 10.1021/ja106283u

Oxidation of methane to methanol and formaldehyde over Co–ZSM-5 molecular sieves: Tuning the reactivity and selectivity by alkaline and acid treatments of the zeolite ZSM-5 agglomerates
journal, February 2011

  • Beznis, Nadzeya V.; van Laak, Adri N. C.; Weckhuysen, Bert M.
  • Microporous and Mesoporous Materials, Vol. 138, Issue 1-3
  • DOI: 10.1016/j.micromeso.2010.09.009

Methane to methanol over copper mordenite: yield improvement through multiple cycles and different synthesis techniques
journal, January 2016

  • Bozbag, Selmi E.; Alayon, Evalyn Mae C.; Pecháček, Jan
  • Catalysis Science & Technology, Vol. 6, Issue 13
  • DOI: 10.1039/C6CY00041J

Reactions of the atomic oxygen radical anion and the synthesis of organic reactive intermediates
journal, November 1992

  • Lee, Jeehiun; Grabowski, Joseph J.
  • Chemical Reviews, Vol. 92, Issue 7
  • DOI: 10.1021/cr00015a007

The active site of low-temperature methane hydroxylation in iron-containing zeolites
journal, August 2016

  • Snyder, Benjamin E. R.; Vanelderen, Pieter; Bols, Max L.
  • Nature, Vol. 536, Issue 7616
  • DOI: 10.1038/nature19059

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects
journal, March 2017


[Cu 2 O] 2+ Active Site Formation in Cu–ZSM-5: Geometric and Electronic Structure Requirements for N 2 O Activation
journal, February 2014

  • Tsai, Ming-Li; Hadt, Ryan G.; Vanelderen, Pieter
  • Journal of the American Chemical Society, Vol. 136, Issue 9
  • DOI: 10.1021/ja4113808

Spectroscopic Definition of the Copper Active Sites in Mordenite: Selective Methane Oxidation
journal, May 2015

  • Vanelderen, Pieter; Snyder, Benjamin E. R.; Tsai, Ming-Li
  • Journal of the American Chemical Society, Vol. 137, Issue 19
  • DOI: 10.1021/jacs.5b02817

Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature
journal, March 2016

  • Tomkins, Patrick; Mansouri, Ali; Bozbag, Selmi E.
  • Angewandte Chemie, Vol. 128, Issue 18
  • DOI: 10.1002/ange.201511065

Cu based zeolites: A UV–vis study of the active site in the selective methane oxidation at low temperatures
journal, December 2005


Partial Oxidation of Methane Over Co-ZSM-5: Tuning the Oxygenate Selectivity by Altering the Preparation Route
journal, November 2009

  • Beznis, Nadzeya V.; Weckhuysen, Bert M.; Bitter, Johannes H.
  • Catalysis Letters, Vol. 136, Issue 1-2
  • DOI: 10.1007/s10562-009-0206-6

Reaction Conditions of Methane-to-Methanol Conversion Affect the Structure of Active Copper Sites
journal, December 2013

  • Alayon, Evalyn Mae C.; Nachtegaal, Maarten; Bodi, Andras
  • ACS Catalysis, Vol. 4, Issue 1
  • DOI: 10.1021/cs400713c

Methane to Methanol: Structure–Activity Relationships for Cu-CHA
journal, October 2017

  • Pappas, Dimitrios K.; Borfecchia, Elisa; Dyballa, Michael
  • Journal of the American Chemical Society, Vol. 139, Issue 42
  • DOI: 10.1021/jacs.7b06472

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

Selective anaerobic oxidation of methane enables direct synthesis of methanol
journal, May 2017

  • Sushkevich, Vitaly L.; Palagin, Dennis; Ranocchiari, Marco
  • Science, Vol. 356, Issue 6337
  • DOI: 10.1126/science.aam9035

Methane to Acetic Acid over Cu-Exchanged Zeolites: Mechanistic Insights from a Site-Specific Carbonylation Reaction
journal, January 2015

  • Narsimhan, Karthik; Michaelis, Vladimir K.; Mathies, Guinevere
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja5106927

Solid-State Ion-Exchanged Cu/Mordenite Catalysts for the Direct Conversion of Methane to Methanol
journal, January 2017


Synthesis of single-site copper catalysts for methane partial oxidation
journal, January 2016

  • Grundner, S.; Luo, W.; Sanchez-Sanchez, M.
  • Chemical Communications, Vol. 52, Issue 12
  • DOI: 10.1039/C5CC08371K

Electronic Structure of the [Cu 3 (μ-O) 3 ] 2+ Cluster in Mordenite Zeolite and Its Effects on the Methane to Methanol Oxidation
journal, September 2017

  • Vogiatzis, Konstantinos D.; Li, Guanna; Hensen, Emiel J. M.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 40
  • DOI: 10.1021/acs.jpcc.7b08714

Understanding and exploiting C–H bond activation
journal, May 2002

  • Labinger, Jay A.; Bercaw, John E.
  • Nature, Vol. 417, Issue 6888
  • DOI: 10.1038/417507a

Modified Lanthanum Catalysts for Oxidative Chlorination of Methane
journal, April 2009


Continuous selective oxidation of methane to methanol over Cu- and Fe-modified ZSM-5 catalysts in a flow reactor
journal, July 2016


Conversion of Methane to Methanol with a Bent Mono(μ-oxo)dinickel Anchored on the Internal Surfaces of Micropores
journal, July 2014

  • Shan, Junjun; Huang, Weixin; Nguyen, Luan
  • Langmuir, Vol. 30, Issue 28
  • DOI: 10.1021/la501184b

A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu–ZSM-5
journal, January 2014

  • Sheppard, T.; Hamill, C. D.; Goguet, A.
  • Chem. Commun., Vol. 50, Issue 75
  • DOI: 10.1039/C4CC02832E

Cu-ZSM-5 Zeolites for the Formation of Methanol from Methane and Oxygen: Probing the Active Sites and Spectator Species
journal, June 2010

  • Beznis, Nadzeya V.; Weckhuysen, Bert M.; Bitter, Johannes H.
  • Catalysis Letters, Vol. 138, Issue 1-2
  • DOI: 10.1007/s10562-010-0380-6

Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, Cu)
journal, November 2016

  • Mahyuddin, M. Haris; Staykov, Aleksandar; Shiota, Yoshihito
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b01721

The Stability of Copper Oxo Species in Zeolite Frameworks
journal, March 2016

  • Vilella, Laia; Studt, Felix
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 10
  • DOI: 10.1002/ejic.201501270

Identification of α-Fe in High-Silica Zeolites on the Basis of ab Initio Electronic Structure Calculations
journal, August 2017


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

Evolution of Iron States and Formation of α-Sites upon Activation of FeZSM-5 Zeolites
journal, April 2002

  • Dubkov, K. A.; Ovanesyan, N. S.; Shteinman, A. A.
  • Journal of Catalysis, Vol. 207, Issue 2
  • DOI: 10.1006/jcat.2002.3552

Theoretical Insights into the Selective Oxidation of Methane to Methanol in Copper-Exchanged Mordenite
journal, May 2016


Factors Controlling the Acidity of Zeolites
journal, December 2014


Distinct activation of Cu-MOR for direct oxidation of methane to methanol
journal, January 2017

  • Kim, Younhwa; Kim, Tae Yong; Lee, Hyunjoo
  • Chemical Communications, Vol. 53, Issue 29
  • DOI: 10.1039/C7CC00467B

Roles of Water Molecules in Modulating the Reactivity of Dioxygen-Bound Cu-ZSM-5 toward Methane: A Theoretical Prediction
journal, March 2016


Understanding trends in C–H bond activation in heterogeneous catalysis
journal, October 2016

  • Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4760

Aspects of Methane Chemistry
journal, June 1995


    Works referencing / citing this record: