Local Structure and Electronic State of Atomically Dispersed Pt Supported on Nanosized CeO2

Matthew Kottwitz, Yuanyuan Li, Robert M. Palomino, Zongyuan Liu, Guangjin Wang, Qin Wu, Jiahao Huang, Janis Timoshenko, Sanjaya D. Senanayake, Mahalingam Balasubramanian, Deyu Lu, Ralph G. Nuzzo, Anatoly I. Frenkel

Research output: Contribution to journalArticlepeer-review

82 Scopus citations

Abstract

Single atom catalysts (SACs) have shown high activity and selectivity in a growing number of chemical reactions. Many efforts aimed at unveiling the structure-property relationships underpinning these activities and developing synthesis methods for obtaining SACs with the desired structures are hindered by the paucity of experimental methods capable of probing the attributes of local structure, electronic properties, and interaction with support - features that comprise key descriptors of their activity. In this work, we describe a combination of experimental and theoretical approaches that include photon and electron spectroscopy, scattering, and imaging methods, linked by density functional theory calculations, for providing detailed and comprehensive information on the atomic structure and electronic properties of SACs. This characterization toolbox is demonstrated here using a model single atom Pt/CeO2 catalyst prepared via a sol-gel-based synthesis method. Isolated Pt atoms together with extra oxygen atoms passivate the (100) surface of nanosized ceria. A detailed picture of the local structure of Pt nearest environment emerges from this work involving the bonding of isolated Pt2+ ions at the hollow sites of perturbed (100) surface planes of the CeO2 support, as well as a substantial (and heretofore unrecognized) strain within the CeO2 lattice in the immediate vicinity of the Pt centers. The detailed information on structural attributes provided by our approach is the key for understanding and improving the properties of SACs.

Original languageEnglish
Pages (from-to)8738-8748
Number of pages11
JournalACS Catalysis
Volume9
Issue number9
DOIs
StatePublished - Sep 6 2019
Externally publishedYes

Funding

R.G.N. and A.I.F. gratefully acknowledge support for this work by the U.S. Department of Energy, Office of Basic Energy Sciences under Grant No. DE-FG02-03ER15476. DRIFTS experiments and reactivity tests were supported by the LDRD 18-047 grant at Brookhaven National Laboratory. STEM characterization was carried out in the Frederick Seitz Materials Research Laboratory Central Research Facilities, University of Illinois. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, and the Scientific Data and Computing Center, a component of the Computational Science Initiative, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704. G.W. thanks the financial support by the National Natural Science Foundation of China (No. 21802037) and Natural Science Foundation of Hubei Province of China (No. 2018CFB669). The authors thank Drs. F. M. F. de Groot, P. Glatzel, and I. Jarrige for useful discussions.

Keywords

  • catalysis
  • ceria
  • multimodal
  • platinum
  • single atom
  • sol-gel

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