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

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:
Grant/Contract Number:
AC02-76SF00515
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
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1426493

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., 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. 2017. "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}
}

Works referenced in this record:

Ab initiomolecular dynamics for liquid metals
journal, January 1993