Single Ru(II) Ions on Ceria as a Highly Active Catalyst for Abatement of NO

作者：Konstantin Khivantsev, Nicholas R. Jaegers, Hristiyan A. Aleksandrov, Inhak Song, Xavier Isidro Pereira-Hernández, Mark Engelhard, Jinshu Tian, Linxiao Chen, Debora Motta Meira, Libor Kovařík, Georgi N. Vayssilov, Yong Wang, János Szanyi · 发表于：Journal of the American Chemical Society · 年份：2023 · DOI：10.1021/jacs.2c09873 · 被引用次数：77 · 研究领域：Catalytic Processes in Materials Science、Catalysis and Oxidation Reactions、Gas Sensing Nanomaterials and Sensors

Atom trapping leads to catalysts with atomically dispersed Ru 1 O 5 sites on (100) facets of ceria, as identified by spectroscopy and DFT calculations. This is a new class of ceria-based materials with Ru properties drastically different from the known M/ceria materials. They show excellent activity in catalytic NO oxidation, a critical step that requires use of large loadings of expensive noble metals in diesel aftertreatment systems. Ru 1 /CeO 2 is stable during continuous cycling, ramping, and cooling as well as the presence of moisture. Furthermore, Ru 1 /CeO 2 shows very high NO x storage properties due to formation of stable Ru–NO complexes as well as a high spill-over rate of NO x onto CeO 2 . Only ∼0.05 wt % of Ru is required for excellent NO x storage. Ru 1 O 5 sites exhibit much higher stability during calcination in air/steam up to 750 °C in contrast to RuO 2 nanoparticles. We clarify the location of Ru(II) ions on the ceria surface and experimentally identify the mechanism of NO storage and oxidation using DFT calculations and in situ DRIFTS/mass spectroscopy. Moreover, we show excellent reactivity of Ru 1 /CeO 2 for NO reduction by CO at low temperatures: only 0.1–0.5 wt % of Ru is sufficient to achieve high activity. Modulation-excitation in situ infrared and XPS measurements reveal the individual elementary steps of NO reduction by CO on an atomically dispersed Ru ceria catalyst, highlighting unique properties of Ru 1 /CeO 2 and its propensity to form oxygen va...