期刊
ACS CATALYSIS
卷 10, 期 8, 页码 4692-4701出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.0c00551
关键词
copper-ceria; oxygen activation mechanism; CO oxidation; operando spectroscopy; time-resolved XAS; non-steady-state kinetics
资金
- Swiss National Science Foundation [200021_140750]
- Russian Science Foundation [17-72-10245]
- President's Grant of Russian Federation for young scientists [MK-2730.2019.2]
- Swiss National Science Foundation (SNF) [200021_140750] Funding Source: Swiss National Science Foundation (SNF)
- Russian Science Foundation [17-72-10245] Funding Source: Russian Science Foundation
Copper-ceria finds applications in various energy-related and environmental catalysts. However, the versatile structure and complex redox activity of this material entangle uncovering structure-activity relationships and distinguishing active species from spectators. In this work, we monitored the dynamic structure of the active sites in a catalyst containing highly dispersed copper-oxo species on ceria during low-temperature CO oxidation using time-resolved X-ray absorption spectroscopy. We quantitatively demonstrate that the CO oxidation mechanism below 90 degrees C involves an oxygen intermediate strongly bound to the active sites as well as the redox activity of Cu2+/Cu+ and Ce4+/Ce3+ couples. The redox activity of cerium is much lower than that of copper; however, both metals change their oxidation states in concert, indicating that oxygen activation involves copper-oxo species in close interaction with ceria. In addition to short-lived Cu+ and Ce3+ intermediates that are generated in the CO oxidation cycle, long-lived Cu+ and Ce3+ species appear in the catalyst under the working conditions. We demonstrate that they do not participate in the main low-temperature CO oxidation mechanism, which is mediated by a strongly bound oxygen intermediate. Finally, our results confirm the high potential of element-specific time-resolved X-ray spectroscopy methods combined with a non-steady-state experimental strategy to uncover the mechanisms of catalytic processes in complex multicomponent systems.
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