Understanding Small-Molecule Interactions in Metal-Organic Frameworks: Coupling Experiment with Theory

• Published in: Advanced materials (Weinheim) 2015-05, Vol.27 (38)
• Main Authors: Lee, Jason S., Vlaisavljevich, Bess, Britt, David K., Brown, Craig M., Haranczyk, Maciej, Neaton, Jeffrey B., Smit, Berend, Long, Jeffrey R., Queen, Wendy L.
• Format: Article
• Language: English
• Subjects: density functional theory; gas adsorption; in- situ characterization; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MATERIALS SCIENCE; metal-organic frameworks; porous
• ISSN: 0935-9648; 1521-4095

Metal-organic frameworks (MOFs) have gained much attention as next generation porous media for various applications, especially gas separations/storage and catalysis. New MOFs are regularly reported; however, to develop better materials in a timely manner for specific applications, the interactions between guest molecules and the internal surface of the framework must first be understood. In this review, we present a combined experimental and theoretical approach that proves essential for the elucidation of small-molecule interactions in a model MOF system known as M2(dobdc) (dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, or Zn), a material whose adsorption properties can be readily tuned via chemical substitution. Here, we additionally show that the study of extensive families like this one can provide a platform to test the efficacy and accuracy of developing computational methodologies in slightly varying chemical environments, a task that is necessary for their evolution into viable, robust tools for screening large numbers of materials.