Abstract
Understanding and controlling nanomaterial structure, chemistry, and defects represents a synthetic and characterization challenge. Metal-organic frameworks (MOFs) have recently been explored as unconventional precursors from which to prepare nanomaterials. Here we use in situ X-ray pair distribution function analysis to probe the mechanism through which MOFs transform into nanomaterials during pyrolysis. By comparing a series of bimetallic MOFs with trimeric node different compositions (Fe3, Fe2Co, and Fe2Ni) linked by carboxylate ligands in a PCN-250 lattice, we demonstrate that the resulting nanoparticle structure, chemistry, and defect concentration depend on the node chemistry of the original MOF. These results suggest that the preorganized structure and chemistry of the MOF offer new potential control over the nanomaterial synthesis under mild reaction conditions. In the case of Fe2Ni-PCN-250, selective extraction of one Ni ion from each node without collapsing the framework (i.e., node-ligand connectivity) leaves a metal-deficient MOF state that may provide a new route to post-synthetically tune the chemistry the MOF and subsequent nanomaterials.
Original language | English (US) |
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Pages (from-to) | 8976-8980 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 24 |
DOIs | |
State | Published - Jun 23 2021 |
Funding
This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012702. This research used resources of the Advanced Photon Source, a U.S. DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357.
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry