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Title: Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.

Abstract

The catalytic activity of oxide-supported metal nanoclusters strongly depends on their size and support. In this study, the origin of morphology transformation and chemical state changes during the oxidative dehydrogenation of cyclohexene was investigated in terms of metal-support interactions. Model catalyst systems were prepared by deposition of size selected subnanometer Co{sub 27{+-}4} clusters on various metal oxide supports (Al{sub 2}O{sub 3}, ZnO and TiO{sub 2} and MgO). The oxidation state and reactivity of the supported cobalt clusters were investigated by temperature programmed reaction (TPRx) and in situ grazing incidence X-ray absorption (GIXAS) during oxidative dehydrogenation of cyclohexene, while the sintering resistance monitored with grazing incidence small angle X-ray scattering (GISAXS). The activity and selectivity of cobalt clusters shows strong dependence on the support. GIXAS reveals that metal-support interaction plays a key role in the reaction. The most pronounced support effect is observed for MgO, where during the course of the reaction in its activity, composition and size dynamically evolving nanoassembly is formed from subnanometer cobalt clusters.

Authors:
; ; ; ; ;  [1];  [2];  [2];  [2]
  1. (Center for Nanoscale Materials)
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1050175
Report Number(s):
ANL/MSD/JA-71563
Journal ID: ISSN 1463-9076; TRN: US201218%%528
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 14; Journal Issue: 26; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
ENGLISH
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; ABSORPTION; CATALYSTS; CHEMICAL STATE; COBALT; DEHYDROGENATION; DEPOSITION; MORPHOLOGY; NANOSTRUCTURES; ORIGIN; OXIDES; PERFORMANCE; SCATTERING; SINTERING; TRANSFORMATIONS; VALENCE

Citation Formats

Lee, S., Di Vece, M., Lee, B., Seifert, S., Winans, R. E., Vajda, S., MSD), XSD), and Yale Univ.). Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.. United States: N. p., 2012. Web. doi:10.1039/C2CP40162B.
Lee, S., Di Vece, M., Lee, B., Seifert, S., Winans, R. E., Vajda, S., MSD), XSD), & Yale Univ.). Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.. United States. doi:10.1039/C2CP40162B.
Lee, S., Di Vece, M., Lee, B., Seifert, S., Winans, R. E., Vajda, S., MSD), XSD), and Yale Univ.). Sun . "Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.". United States. doi:10.1039/C2CP40162B.
@article{osti_1050175,
title = {Oxidative dehydrogenation of cyclohexene on size selected subnanometer cobalt clusters: improved catalytic performance via structural fluxionality of cluster-assembled nanostructures.},
author = {Lee, S. and Di Vece, M. and Lee, B. and Seifert, S. and Winans, R. E. and Vajda, S. and MSD) and XSD) and Yale Univ.)},
abstractNote = {The catalytic activity of oxide-supported metal nanoclusters strongly depends on their size and support. In this study, the origin of morphology transformation and chemical state changes during the oxidative dehydrogenation of cyclohexene was investigated in terms of metal-support interactions. Model catalyst systems were prepared by deposition of size selected subnanometer Co{sub 27{+-}4} clusters on various metal oxide supports (Al{sub 2}O{sub 3}, ZnO and TiO{sub 2} and MgO). The oxidation state and reactivity of the supported cobalt clusters were investigated by temperature programmed reaction (TPRx) and in situ grazing incidence X-ray absorption (GIXAS) during oxidative dehydrogenation of cyclohexene, while the sintering resistance monitored with grazing incidence small angle X-ray scattering (GISAXS). The activity and selectivity of cobalt clusters shows strong dependence on the support. GIXAS reveals that metal-support interaction plays a key role in the reaction. The most pronounced support effect is observed for MgO, where during the course of the reaction in its activity, composition and size dynamically evolving nanoassembly is formed from subnanometer cobalt clusters.},
doi = {10.1039/C2CP40162B},
journal = {Physical Chemistry Chemical Physics},
issn = {1463-9076},
number = 26,
volume = 14,
place = {United States},
year = {2012},
month = {1}
}