Please use this identifier to cite or link to this item: http://hdl.handle.net/1959.13/808854

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Title
In situ XAS and IR studies on Cu:SAPO-5 and Cu:SAPO-11: the contributory role of monomeric linear copper(I) species in the selective catalytic reduction of NOᵪ by propene
Author/Creator
Mathisen, Karina;  Stockenhuber, Michael;  Nicholson, David G.
Institution
The University of Newcastle. Faculty of Engineering & Built Environment, School of Engineering
Description
Cu:SAPO-5 and Cu:SAPO-11 were prepared by conventional and hydrothermal ion exchange. Copper incorporation is increased six-fold by hydrothermal ion exchange relative to conventional methods. In all cases, the amount of copper taken up by SAPO-11 is superior to uptake in SAPO-5. Copper is divalent and in tetragonally-distorted octahedral environments in the as-prepared samples independent of the method of incorporation for both systems. The local structures about the metal and the valence states associated with the different steps in the selective catalytic reduction of NOᵪ in the presence of propene (SCR-HC) have been investigated using X-ray absorption spectroscopy (XAS). For both the Cu:SAPO-5 and Cu:SAPO-11 systems, heating in helium partially autoreduces copper(II) to copper(I). Following activation in oxygen, propene causes further reduction to copper(I) in all four samples as shown by the evolution of an intense pre-edge diagnostic feature. XANES analysis reveal this to be characteristic of monomeric linear two coordinate copper(I) species. This is a prime example of a pre-edge peak with such a high intensity being observed in the solid state. This is supported by IR where peaks attributed to bidentate copper were observed for Cu:SAPO-11/HT. For all four samples NOᵪ partially reoxidises the copper(I) formed in the helium and propene steps. Ion exchanged Cu:SAPO-5 and Cu:SAPO-11 exhibit low activity in reducing NOᵪ by propene in an oxygen rich environment. The role of the copper ion during NO adsorption was studied using in situ infra red spectroscopy. The activity of copper exchanged materials is governed by both the degree of reducibility of copper(II) and the ease of reversing the valence states with the structural characteristics of the parent materials playing a crucial role.
Relation
Physical Chemistry Chemical Physics Vol. 11, Issue 26, p. 5476-5488
Publisher Link
http://dx.doi.org/10.1039/b902491c
Date
2009
Publisher
Royal Society of Chemistry
Keyword(s)
hydrothermal ion exchange;  X-ray absorption spectroscopy;  monomeric linear copper;  copper
Resource Type
journal article
Identifier
http://hdl.handle.net/1959.13/808854
Identifier
ISSN:1463-9076
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Subject
"Physical Chemistry Chemical Physics"
 
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