Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8

Zhang, Chenyang; Han, Chu; Sholl, David S.; Schmidt, J. R.

doi:10.1021/acs.jpclett.5b02683

Computational Characterization of Defects in Metal–Organic Frameworks: Spontaneous and Water-Induced Point Defects in ZIF-8

Journal Article · Fri Jan 15 00:00:00 EST 2016 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.5b02683· OSTI ID:1371131

Zhang, Chenyang ^[1]; Han, Chu ^[2]; Sholl, David S. ^[2]; Schmidt, J. R. ^[1]

Univ. of Wisconsin, Madison, WI (United States)
Georgia Inst. of Technology, Atlanta, GA (United States)

Zeolitic imidazolate frameworks (ZIFs) are an important class of porous crystalline metal–organic framework (MOF) materials that have attracted widespread attention for applications ranging from gas adsorption and separation to catalysis. Although the bulk crystal structures of MOFs are typically well-characterized, comparatively little is known regarding MOF defect structures. Drawing on analogies with conventional silicon-based zeolites, we utilize computational methods to examine the structure and stability of putative point-defect structures (including vacancies, substitutions, and “dangling” linkers) within the prototypical ZIF-8 structure. Considering both postsynthetic (gas-phase) and synthetic (solution-phase) conditions, we find that several of the defect structures lie low in energy relative to the defect-free parent crystal, with barriers to defect formation that are large but surmountable under relevant temperatures. Furthermore, these results are consistent with prior experimental observations of ZIF stability and reactivity and suggest that defects may play an important role in influencing the long-term stability of MOFs under conditions that include exposure to water vapor and trace contaminants such as acid gases.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)

Sponsoring Organization:: National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); UW-Madison Center for High Throughput Computing (CHTC)

Grant/Contract Number:: SC0012577

OSTI ID:: 1371131

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 3 Vol. 7; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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