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

Jason S Lee; Bess Vlaisavljevich; David K Britt; Craig M Brown; Maciej Haranczyk; Jeffrey B Neaton; Berend Smit; Jeffrey R Long; Wendy L Queen

doi:10.1002/adma.201500966

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

Adv Mater. 2015 Oct 14;27(38):5785-96. doi: 10.1002/adma.201500966. Epub 2015 May 28.

Authors

Jason S Lee^{1

2}, Bess Vlaisavljevich², David K Britt¹, Craig M Brown^{3

4}, Maciej Haranczyk⁵, Jeffrey B Neaton^{1

6}, Berend Smit^{2

7}, Jeffrey R Long^{8

9}, Wendy L Queen^{1

7}

Affiliations

¹ The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.
² Department of Chemical and Biomolecular Engineering, University of California, Berkeley, CA, 94720, USA.
³ National Institute of Standards and Technology, Center for Neutron Research, Gaithersburg, MD, 20899, USA.
⁴ Department of Chemical Engineering, University of Delaware, Newark, DE, 19716, USA.
⁵ Computational Research Division Lawrence, Berkeley National Laboratory, Berkeley, CA, 94720, USA.
⁶ Department of Physics, University of California, Berkeley, CA, 94720, USA.
⁷ Department Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015, CH, Lausanne, Switzerland.
⁸ Department of Chemistry, University of California, Berkeley, CA, 94720, USA.
⁹ Division of Materials Sciences, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA.

PMID: 26033176
DOI: 10.1002/adma.201500966

Abstract

Metal-organic frameworks (MOFs) have gained much attention as next-generation porous media for various applications, especially gas separation/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. A combined experimental and theoretical approach is presented, which proves essential for the elucidation of small-molecule interactions in a model MOF system known as M2 (dobdc) (dobdc(4-) = 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. It is additionally shown 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.

Keywords: density functional theory; gas adsorption; in situ characterization; metal-organic frameworks; porous.