Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution

Sanchez, Sergio I.; Small, Matthew W.; Zuo, Jian-min; Nuzzo, Ralph G.

doi:10.1021/ja9020952

Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution

Journal Article · Thu May 28 04:00:00 EDT 2009 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja9020952· OSTI ID:1876401

Sanchez, Sergio I. ^[1]; Small, Matthew W. ^[2]; Zuo, Jian-min ^[2]; Nuzzo, Ralph G. ^[2]

Univ. of Illinois at Urbana-Champaign, IL (United States); University of Illinois
Univ. of Illinois at Urbana-Champaign, IL (United States)

We describe the results of a study at atomic resolution of the structures exhibited by polymer-capped monometallic and bimetallic Pt and Pd nanoclusters—models for nanoscale material electrocatalysts—as carried out using an aberration-corrected scanning transmission electron microscope (STEM). The coupling of sub-nanometer resolution with Z-contrast measurements provides unprecedented insights into the atomic structures and relative elemental speciation of Pt and Pd within these clusters. The work further defines the nature of deeply quenched states that prevent facile conversions of core–shell motifs to equilibrium alloys and the nature of nonidealities such as twinning (icosahedral cores) and atomic segregation that these structures can embed. The nature of the facet structure present in these model systems is revealed by theory directed modeling in which experimental intensity profiles obtained in Z-contrast measurements at atomic resolution are compared to simulated intensity profiles using theoretically predicted cluster geometries. These comparisons show close correspondences between experiment and model and highlight striking structural complexities in these systems that are compositionally sensitive and subject to amplification by subsequent cluster growth processes. Here, the work demonstrates an empowering competency in nanomaterials research for STEM measurements carried out using aberration corrected microscopes, approaches that hold considerable promise for characterizing the structure of these and other important catalytic materials systems at the atomic scale.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: FG02-07ER46471; FG02-03ER15476; FG02-01ER45923; FG02-07ER46453

OSTI ID:: 1876401

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 24 Vol. 131; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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