Structural Tuning of Copper Oxide Reducibility in the Presence of Atomically Dispersed Metals
EMSL Project ID
51182
Abstract
Catalytic surfaces are prone to reconstruction depending on the adsorbates present, catalyst coverage, temperature, and other environmental factors. Through model studies, we can generate trends as to how different oxide configurations interact with precious metal single atoms, which would otherwise be more time consuming if conducted experimentally. Cu is a relatively affordable and abundant resource in which its oxide is potentially reducible. In our previous study, atomically dispersed Pt atoms on a particular CuxO film on Cu(111) has been found to be active for CO oxidation through the Mars van Krevelen (MvK) mechanism. However, not all single-site Pt catalysts on a thin oxide film on metallic Cu have shown the same activity for the same reaction. The research objective of this work is to theoretically characterize how variations within the Cu oxide facets electronically interact with a precious metal adatom. The central hypothesis is that we can tune the activity of precious metal adatoms for CO oxidation by controlling the Cu oxide structure. We aim to understand how the presence of precious metal adatoms influence the reducibility and catalytic activity of the Cu oxide support in different coordination environments. To accomplish the research objective, we will conduct a systematic study generating trends of oxide reducibility, CO oxidation reaction energies, and surface charge transfer against various Pt-support combinations. These results can then give insights toward the design for reducible supports which stabilize active single atoms for CO oxidation. Throughout these calculations, we will be validating our model with available experimental data provided by our collaborators by the Brookhaven National Laboratory and Tufts University to ensure the applicability of the developed theories. By understanding how different copper oxide surfaces interact with precious single atoms, we will gain insights for the local geometry suitable for increasing the oxide’s reducibility and stability. Such results will guide us as to how we can replace precious metals in traditional three-way catalytic converter catalysts with cheaper and more abundant materials.
Project Details
Start Date
2019-10-01
End Date
2020-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
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Schilling A.C., K.J. Groden, J.P. Simonovis, A. Hunt, R.T. Hannagan, V. Cinar, and J. McEwen, et al. 2020. "Accelerated Cu2O Reduction by Single Pt Atoms at the Metal-Oxide Interface§." ACS Catalysis 10, no. 7:4215–4226. PNNL-SA-151943. doi:10.1021/acscatal.9b05270
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