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

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.