Abstract
Postsynthetic strategies for modifying metal-organic frameworks (MOFs) have proven to be an incredibly powerful approach for expanding the scope and functionality of these materials. Previously, we reported on the postsynthetic exchange (PSE) of metal ions and ligands in the University of Oslo (UiO) series of MOFs. Detailed characterization by several analytical methods, most notably inductively coupled plasma mass spectrometry and transmission electron microscopy reveal that metal ion deposition on the surface of these MOFs occurs in the form of nanoscale metal oxides, rather than yielding exchanged metal sites within the MOFs, as was previously reported. By contrast, these combined analytical methods do confirm that ligand-based PSE can occur in these MOFs. These findings provide new insight into the postsynthetic manipulation of MOF materials, highlight the importance of rigorously characterizing these materials to correctly assign their composition and structure, and provide a new route to making hybrid solids with a MOF@metal oxide architecture.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 1348-1357 |
| Number of pages | 10 |
| Journal | Journal of the American Chemical Society |
| Volume | 140 |
| Issue number | 4 |
| DOIs | |
| State | Published - Jan 31 2018 |
Funding
We acknowledge financial support from the Army Research Office, Department of Army Material command, under award no. W911NF-15-1-0189. This work was performed in part at the San Diego Nanotechnology Infrastructure (SDNI) of U.C. San Diego, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (grant ECCS-1542148). L.R.P. is supported by the National Institute of Biomedical Imaging and Bioengineering of the National Institutes of Health under award number F32EB021859. A portion of the research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the U.S. Department of Energy (DOE), Office of Biological and Environmental Research, and located at Pacific Northwest National Laboratory (PNNL). The EMSL electron microscopy facility was accessed through EMSL user proposal no. 49590. PNNL is operated by Battelle 454 for DOE under contract DE-AC05-76RL01830. We thank Dr. James Evans and Trevor Moser for assistance in STEM-EDX characterization done at PNNL-EMSL. We thank the cryo-electron microscopy facility supported by Prof. Timothy Baker (U.C. San Diego) funded by the National Institutes of Health and Dr. James Bower for assistance in low-dose HRTEM imaging. We thank the Environmental and Complex Analysis Laboratory (Dr. Richard E. Cochran, U.C. San Diego) for assistance with ICP-MS experiments. STEM-EELS was conducted at the SuperSTEM Laboratory, the U.K. National Facility for Aberration-Corrected STEM, supported by the Engineering and Physical Sciences Research Council (EPSRC).
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry