Abstract
The prospect of using copper oxide nanoclusters grown by atomic layer deposition on a porphyrin support for selective oxidation of methane to methanol was examined by means of density functional theory (DFT) calculations. Ab initio thermodynamic analysis indicates that an active site in the form of Cu(μ-O)Cu can be stabilized by activation in O2 at 465 K. Furthermore, a moderate methane activation energy barrier (Ea = 54 kJ/mol) is predicted, and the hydrogen abstraction activity of the active site could be attributed to the radical character of the bridging oxygen. Methanol extraction in this system is limited by a thermodynamic barrier to desorption of ΔG = 57 kJ/mol at 473 K; however, desorption can be facilitated by the addition of water in a “stepped conversion” process. Overall, our results indicate similar activity between porphyrin-supported copper oxide nanoclusters and existing Cu-exchanged zeolites and provide a computational proof-of-concept for utilizing functionalized organic linkers in metal-organic frameworks (MOFs) for selective oxidation of methane to methanol.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2-9 |
| Number of pages | 8 |
| Journal | Catalysis Today |
| Volume | 312 |
| DOIs | |
| State | Published - Aug 15 2018 |
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 National Energy Research Scientific Computing Center (NERSC), 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 , and the Quest high performance computing facility at Northwestern University .
Keywords
- Atomic layer deposition
- C1 chemistry
- Copper
- DFT
- Methane to methanol
- Porphyrin
ASJC Scopus subject areas
- Catalysis
- General Chemistry