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 Zr^IV substitution with heavier Ce^IV, 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.