Computational Screening of Roles of Defects and Metal Substitution on Reactivity of Different Single- vs Double-Node Metal-Organic Frameworks for Sarin Decomposition

Mohammad R. Momeni, Chris Cramer

Research output: Contribution to journalArticle

Abstract

Understanding how different factors affect the electronic properties of metal-organic frameworks (MOFs) is critical to understanding their potential for catalysis and to serve as catalyst supports. In this work, periodic dispersion-corrected quantum mechanical calculations are performed to assess the catalytic activity of different Zr6 vs Zr12 MOFs for the heterogeneous catalytic hydrolysis of the chemical warfare agent sarin. Using a comprehensive series of extended periodic models capable of capturing long-range sarin/water/framework interactions in both Zr6 and Zr12 MOFs, the effects of numbers and morphologies of defective sites, as well as ZrIV substitution with heavier CeIV, are thoroughly investigated. Our calculations show that hydrogen bonds involving both metal-oxide nodes and organic linkers can play important roles in the catalysis. Insights derived from this work should inform the design and realization of more effective and robust next-generation MOF-based heterogeneous catalysts.

Original languageEnglish (US)
Pages (from-to)15157-15165
Number of pages9
JournalJournal of Physical Chemistry C
Volume123
Issue number24
DOIs
StatePublished - Jun 20 2019

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Sarin
Screening
Substitution reactions
screening
reactivity
Metals
substitutes
Decomposition
decomposition
Defects
defects
metals
catalysis
Catalysis
chemical warfare
catalysts
Chemical Warfare Agents
Chemical warfare
metal oxides
hydrolysis

Cite this

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abstract = "Understanding how different factors affect the electronic properties of metal-organic frameworks (MOFs) is critical to understanding their potential for catalysis and to serve as catalyst supports. In this work, periodic dispersion-corrected quantum mechanical calculations are performed to assess the catalytic activity of different Zr6 vs Zr12 MOFs for the heterogeneous catalytic hydrolysis of the chemical warfare agent sarin. Using a comprehensive series of extended periodic models capable of capturing long-range sarin/water/framework interactions in both Zr6 and Zr12 MOFs, the effects of numbers and morphologies of defective sites, as well as ZrIV substitution with heavier CeIV, are thoroughly investigated. Our calculations show that hydrogen bonds involving both metal-oxide nodes and organic linkers can play important roles in the catalysis. Insights derived from this work should inform the design and realization of more effective and robust next-generation MOF-based heterogeneous catalysts.",
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AB - Understanding how different factors affect the electronic properties of metal-organic frameworks (MOFs) is critical to understanding their potential for catalysis and to serve as catalyst supports. In this work, periodic dispersion-corrected quantum mechanical calculations are performed to assess the catalytic activity of different Zr6 vs Zr12 MOFs for the heterogeneous catalytic hydrolysis of the chemical warfare agent sarin. Using a comprehensive series of extended periodic models capable of capturing long-range sarin/water/framework interactions in both Zr6 and Zr12 MOFs, the effects of numbers and morphologies of defective sites, as well as ZrIV substitution with heavier CeIV, are thoroughly investigated. Our calculations show that hydrogen bonds involving both metal-oxide nodes and organic linkers can play important roles in the catalysis. Insights derived from this work should inform the design and realization of more effective and robust next-generation MOF-based heterogeneous catalysts.

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