Atmosphere-Induced Transient Structural Transformations of Pd-Cu and Pt-Cu Alloy Nanocrystals.

Autor: Pasquale L; Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.; Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genova, Italy., Najafishirtari S; Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy., Brescia R; Electron Microscopy Facility, Istituto Italiano di Tecnologia, Via Morego 30 16163, Genova, Italy., Scarpellini A; Electron Microscopy Facility, Istituto Italiano di Tecnologia, Via Morego 30 16163, Genova, Italy., Demirci C; Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.; Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova, Via Dodecaneso 31, 16146 Genova, Italy., Colombo M; Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy., Manna L; Department of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.
Jazyk: angličtina
Zdroj: Chemistry of materials : a publication of the American Chemical Society [Chem Mater] 2021 Nov 23; Vol. 33 (22), pp. 8635-8648. Date of Electronic Publication: 2021 Nov 10.
DOI: 10.1021/acs.chemmater.1c02377
Abstrakt: We have investigated the transformations of colloidal Pd-Cu and Pt-Cu bimetallic alloy nanocrystals (NCs) supported on γ-Al 2 O 3 when exposed to a sequence of oxidizing and then reducing atmospheres, in both cases at high temperature (350 °C). A combination of in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopy was employed to probe the NC surface chemistry and structural/compositional variations in response to the different test conditions. Depending on the type of noble metal in the bimetallic NCs (whether Pd or Pt), different outcomes were observed. The oxidizing treatment on Pd-Cu NCs led to the formation of a PdCuO mixed oxide and PdO along with a minor fraction of CuO x species on the support. The same treatment on Pt-Cu NCs caused a complete dealloying between Pt and Cu, forming separate Pt NCs with a minor fraction of PtO NCs and CuO x species, the latter finely dispersed on the support. The reducing treatment that followed the oxidizing treatment largely restored the Pd-Cu alloy NCs, although with a residual fraction of CuO x species remaining. Similarly, Pt-Cu NCs were partially restored but with a large fraction of CuO x species still located on the support. Our results indicate that the noble metal present in the bimetallic Cu-based alloy NCs has a strong influence on the dealloying/migrations/realloying processes occurring under typical heterogeneous catalytic reactions, elucidating the structural/compositional variations of these NCs depending on the atmospheres to which they are exposed.
Competing Interests: The authors declare no competing financial interest.
(© 2021 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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