Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction

Yuanyuan Li; Matthew Kottwitz; Joshua L Vincent; Michael J Enright; Zongyuan Liu; Lihua Zhang; Jiahao Huang; Sanjaya D Senanayake; Wei-Chang D Yang; Peter A Crozier; Ralph G Nuzzo; Anatoly I Frenkel

doi:10.1038/s41467-021-21132-4

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction

Nat Commun. 2021 Feb 10;12(1):914. doi: 10.1038/s41467-021-21132-4.

Authors

Yuanyuan Li¹, Matthew Kottwitz², Joshua L Vincent³, Michael J Enright², Zongyuan Liu⁴, Lihua Zhang⁵, Jiahao Huang⁶, Sanjaya D Senanayake⁴, Wei-Chang D Yang^{7

8}, Peter A Crozier³, Ralph G Nuzzo^{2

9}, Anatoly I Frenkel^{6

4}

Affiliations

¹ Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, 11794, USA. Yuanyuan.li@stonybrook.edu.
² Department of Chemistry, University of Illinois, Urbana, IL, 61801, USA.
³ School for Engineering of Matter, Transport and Energy, Arizona State University, Tempe, AZ, 85287-6106, USA.
⁴ Chemistry Division, Brookhaven National Laboratory, Upton, NY, 11973, USA.
⁵ Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA.
⁶ Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, 11794, USA.
⁷ Physical Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, 20899, USA.
⁸ Institute for Research in Electronics and Applied Physics & Maryland NanoCenter, University of Maryland, College Park, MD, 20742, USA.
⁹ Surface and Corrosion Science, School of Engineering Sciences in Chemistry, Biotechnology and Health, KTH Royal Institute of Technology, Drottning Kristinasväg 51, 100 44, Stockholm, Sweden.

Abstract

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding-perhaps most importantly the temporal dynamic changes occurring therein-serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO₂ system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt⁰ - O vacancy-Ce³⁺ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.