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 prop-erties of metal-organic frameworks (MOFs) is critical to under-standing their potential for catalysis and to serve as catalyst supports. In this work, periodic dispersion corrected PBE cal-culations are performed to assess the catalytic activity of dif-ferent Zr6 vs Zr12 metal-organic frameworks (MOFs) for the heterogeneous catalytic hydrolysis of the chemical warfare agent (CWA) sarin. Using a comprehensive series of extended periodic models capable of capturing long-range sar-in/water/framework interactions in both Zr6 and Zr12 MOFs, the effect of numbers and morphologies of defective sites as well as ZrIV substitution with heavier CeIV are thoroughly in-vestigated. Our calculations show that hydrogen bonds in-volving 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 effec-tive and robust next-generation MOF-based heterogeneous catalysts.