Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–x Pt x Clusters under H 2 and CO + H 2 Atmospheres

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; Tyo, Eric C.; Pellin, Michael J.; Reinhart, Benjamin; Seifert, Sönke; Chen, Xinqi; Dupuis, Veronique; Vajda, Stefan

doi:10.1021/acs.jpcc.6b06483

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co _1–x Pt _x Clusters under H ₂ and CO + H ₂ Atmospheres

Journal Article · Thu Sep 29 04:00:00 EDT 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b06483· OSTI ID:1392497

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; Tyo, Eric C.; Pellin, Michael J.; Reinhart, Benjamin; Seifert, Sönke; Chen, Xinqi; Dupuis, Veronique; Vajda, Stefan

Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H-2 up to 225 degrees C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the dusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the dusters. For example, a low Pt/Co ratio (x <= 0.5) facilitates the formation of Co(OH)(2), whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co-Pt core-shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1-xPtx alloy dusters. The obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.

Research Organization:: Argonne National Laboratory (ANL)

Sponsoring Organization:: USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division

DOE Contract Number:: AC02-06CH11357

OSTI ID:: 1392497

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 38 Vol. 120; ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

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