Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

Khivantsev, Konstantin; Vargas, Carlos Garcia; Tian, Jinshu; Kovarik, Libor; Jaegers, Nicholas R.; Szanyi, Janos; Wang, Yong

doi:10.1002/ange.202010815

Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

Journal Article · Wed Oct 28 04:00:00 EDT 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202010815· OSTI ID:1786159

^[1]; Vargas, Carlos Garcia ^[2]; Tian, Jinshu ^[1]; Kovarik, Libor ^[1]; Jaegers, Nicholas R. ^[2]; Szanyi, Janos ^[1]; Wang, Yong ^[2]

Institute for Integrated Catalysis Pacific Northwest National Laboratory Richland WA 99352 USA
Institute for Integrated Catalysis Pacific Northwest National Laboratory Richland WA 99352 USA, Voiland School of Chemical Engineering and Bioengineering Washington State University Pullman WA 99163 USA

Abstract

We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh ^I complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh ₁ /CeO ₂ achieve full NO conversion with a turn‐over‐frequency (TOF) of around 330 h ⁻¹ per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N ₂ with N ₂ O being the minor product. The presence of water promotes low‐temperature activity of 0.1 wt % Rh ₁ /CeO ₂ . In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH ₃ formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC06-76RL01830

OSTI ID:: 1786159

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 1 Vol. 133; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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