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

Momeni, M. R.; Cramer, C. J.
J. Phys. Chem. C 2019, 123, 15157 (doi:10.1021/acs.jpcc.9b03817).

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 PBE calculations are performed to assess the catalytic activity of different 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 sarin/water/framework interactions in both Zr₆ and Zr₁₂ MOFs, the effect 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.