Tailoring the Local Environment of Platinum in Single-Atom Pt1 /CeO2 Catalysts for Robust Low-Temperature CO Oxidation

Dong Jiang; Yonggang Yao; Tangyuan Li; Gang Wan; Xavier Isidro Pereira-Hernández; Yubing Lu; Jinshu Tian; Konstantin Khivantsev; Mark H Engelhard; Chengjun Sun; Carlos E García-Vargas; Adam S Hoffman; Simon R Bare; Abhaya K Datye; Liangbing Hu; Yong Wang

doi:10.1002/anie.202108585

Tailoring the Local Environment of Platinum in Single-Atom Pt₁ /CeO₂ Catalysts for Robust Low-Temperature CO Oxidation

Angew Chem Int Ed Engl. 2021 Dec 6;60(50):26054-26062. doi: 10.1002/anie.202108585. Epub 2021 Sep 9.

Authors

Dong Jiang¹, Yonggang Yao^{2

3}, Tangyuan Li², Gang Wan⁴, Xavier Isidro Pereira-Hernández¹, Yubing Lu⁵, Jinshu Tian⁵, Konstantin Khivantsev⁵, Mark H Engelhard⁵, Chengjun Sun⁶, Carlos E García-Vargas¹, Adam S Hoffman⁴, Simon R Bare⁴, Abhaya K Datye⁷, Liangbing Hu², Yong Wang^{1

5}

Affiliations

¹ The Gene and Linda Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, WA, 99164, USA.
² Department of Materials Science and Engineering, University of Maryland, College Park, MD, 20742, USA.
³ Current address: State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China.
⁴ Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, 94025, USA.
⁵ Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, WA, 99354, USA.
⁶ X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Lemont, IL, 60439, USA.
⁷ Department of Chemical and Biological Engineering and Center for Micro-Engineered Materials, University of New Mexico, Albuquerque, NM, 87131, USA.

PMID: 34346155
DOI: 10.1002/anie.202108585

Abstract

A single-atom Pt₁ /CeO₂ catalyst formed by atom trapping (AT, 800 °C in air) shows excellent thermal stability but is inactive for CO oxidation at low temperatures owing to over-stabilization of Pt²⁺ in a highly symmetric square-planar Pt₁ O₄ coordination environment. Reductive activation to form Pt nanoparticles (NPs) results in enhanced activity; however, the NPs are easily oxidized, leading to drastic activity loss. Herein we show that tailoring the local environment of isolated Pt²⁺ by thermal-shock (TS) synthesis leads to a highly active and thermally stable Pt₁ /CeO₂ catalyst. Ultrafast shockwaves (>1200 °C) in an inert atmosphere induced surface reconstruction of CeO₂ to generate Pt single atoms in an asymmetric Pt₁ O₄ configuration. Owing to this unique coordination, Pt₁ ^δ+ in a partially reduced state dynamically evolves during CO oxidation, resulting in exceptional low-temperature performance. CO oxidation reactivity on the Pt₁ /CeO₂ _TS catalyst was retained under oxidizing conditions.

Keywords: CO oxidation; metal-support interactions; platinum; single-atom catalysis; thermal-shock synthesis.

Abstract

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