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Impact of defects on the decomposition of chemical warfare agent simulants in Zr‐based metal organic frameworks
Author(s) -
Vo Minh Nguyen,
Ruffley Jonathan P.,
Johnson J. Karl
Publication year - 2021
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.17156
Subject(s) - sbus , physisorption , metal organic framework , decomposition , chemistry , desorption , dimethyl methylphosphonate , chemisorption , zirconium , linker , nanotechnology , inorganic chemistry , materials science , organic chemistry , adsorption , computer science , operating system
Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO‐67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO‐67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO‐67 samples. We present density functional theory calculations showing that SBU sites having two‐adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.