Abstract
Exposure of the metal-organic zeolitic imidazolate framework-8 (ZIF-8) to humid SOx gas cleaves Zn-N bonds, leading to framework disorder and a corresponding decrease in pore accessibility. This work shows that framework disorder exhibits a critical behavior with respect to water concentration in the gas stream. While the quantity of sulfate adsorbed at Zn nodes is at or below the detection threshold for the X-ray pair distribution function technique, precluding direct observation of the adsorbate, powder diffraction reveals clear structural alterations. The onset of linker cleavage correlates to a large microstrain that diminishes as framework disorder increases. Energy-dispersive X-ray spectroscopy shows that the sulfur distribution throughout representative grains is uniform, implying the structure transformation is homogeneously nucleated and not dependent upon gas diffusion kinetics.
| Original language | English |
|---|---|
| Pages (from-to) | 9736-9741 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry C |
| Volume | 126 |
| Issue number | 23 |
| DOIs | |
| State | Published - Jun 16 2022 |
Funding
The material synthesis and physical property measurements were supported as part of UNCAGE-ME, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0012577. Structure analysis by P.C.M. was jointly supported by UNCAGE-ME and the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences Early Career Research Program Award KC040602, under Contract DE-AC05-00OR22725. M.R.R. acknowledges the U.S. Department of Energy (DOE) Office of Fossil Energy and Carbon Management for research funding and the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract DE-AC02-05CH11231 for access to supercomputing resources. This research used resources of the Advanced Photon Source, a U.S. Department of Energy Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357. The authors gratefully acknowledge Palani Raja Jothi for acquisition of the SEM-EDS data present in the Supporting Information .