Abstract
Density functional theory is used to study the tunability of trigonal prismatic SBUs found in metal-organic frameworks (MOFs) such as MIL-100, MIL-101, and PCN-250/MIL-127 of chemical composition M3+2M2+(μ3-O)(RCOO)6 for the partial oxidation of methane to methanol. We performed a combinatorial screening by varying the composition of the trimetallic node (M13+)2(M22+) (where M1 and M2 = V, Cr, Mn, Fe, Co, and Ni) and calculated the reaction pathway on both M1 and M2 sites. The systematic replacement of metals in the trimetallic cluster allowed us to study the influence of spectator atoms on the catalytic activity of a specific metal site in the cluster toward the N2O activation and C-H bond activation steps of the reaction. In the screening, we identified the top-performing node compositions with predicted barriers lower than those already reported for experimentally tested MOFs with trigonal prismatic SBUs. This work demonstrates the opportunity to tune the catalytic activity of MOFs for redox reactions by changing their metal node composition.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 28217-28231 |
| Number of pages | 15 |
| Journal | ACS Applied Materials and Interfaces |
| Volume | 12 |
| Issue number | 25 |
| DOIs | |
| State | Published - Jun 24 2020 |
Funding
M.B. would like to thank the Quest High Performance Computing Cluster, which is maintained by the Northwestern University Information Technology, and the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. M.B. would like to additionally thank the National Science Foundation for a Graduate Research Fellowship.
Keywords
- C-H bond activation
- catalysis
- density functional theory
- metal-organic framework
- methane
- methanol
- partial oxidation
ASJC Scopus subject areas
- General Materials Science