Influence of the Preparation Method, Outgassing Treatment, and Adsorption of NO and/or O2 on the Cu2+ Species in Cu-ZSM-5

An EPR Study

J. Soria, A. Martínez-Arias, A. Martínez-Chaparro, J. C. Conesa, Z. Schay

Research output: Contribution to journalArticle

22 Citations (Scopus)

Abstract

Two Cu2+-loaded ZSM-5 zeolites prepared by ion exchange from liquid solution (LS) and solid-state reaction (SR) are studied by EPR after vacuum treatments at several temperatures, Tv, up to 413 K and subsequent NO and/or O2 adsorption. In addition to the changes in Cu2+ coordination upon dehydration, from octahedral to square pyramidal and planar, outgassing produced in sample LS a decrease of the Cu2+ EPR signal, initiated by brief outgassing at 298 K and reaching a maximum (ca. 75% of the total copper not detected) for Tv=383 K. This is ascribed to fast spin relaxation, due either to a ligand geometry effect or to the establishment of copper-copper interactions. Subsequent NO adsorption at 298 K generated (Cu-NO)+ complexes, apparently by reaction of square planar Cu2+ (possibly assisted by water or OH- still present), while NO and O2 coadsorption led to a large change, all copper now being EPR-visible either as a sharp signal for a square planar species or as a broad band due to spin-interacting Cu2+. For sample SR, the resolved Cu2+ EPR signals, representing ca. 25% of the total copper, behave similarly to those found in sample LS (except that their overall intensity decreases little upon outgassing), but most copper exists as Cu-oxide clusters giving a broad EPR signal. The latter, resulting from the solid-state preparation method, seem scarcely reactive on adsorption of NO or NO+O2; they may be connected with the lower catalytic activity in NO decomposition previously observed for this latter sample.

Original languageEnglish
Pages (from-to)352-363
Number of pages12
JournalJournal of Catalysis
Volume190
Issue number2
DOIs
Publication statusPublished - Mar 10 2000

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outgassing
Degassing
Paramagnetic resonance
Copper
Adsorption
copper
preparation
adsorption
Liquids
liquids
solid state
Zeolites
Solid state reactions
Dehydration
zeolites
dehydration
Oxides
catalytic activity
Catalyst activity
Ion exchange

Keywords

  • Clustering
  • Coordination
  • Copper
  • Dehydration
  • EPR
  • Nitric oxide
  • Solid-state exchange
  • ZSM-5 zeolite

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Cite this

Influence of the Preparation Method, Outgassing Treatment, and Adsorption of NO and/or O2 on the Cu2+ Species in Cu-ZSM-5 : An EPR Study. / Soria, J.; Martínez-Arias, A.; Martínez-Chaparro, A.; Conesa, J. C.; Schay, Z.

In: Journal of Catalysis, Vol. 190, No. 2, 10.03.2000, p. 352-363.

Research output: Contribution to journalArticle

Soria, J. ; Martínez-Arias, A. ; Martínez-Chaparro, A. ; Conesa, J. C. ; Schay, Z. / Influence of the Preparation Method, Outgassing Treatment, and Adsorption of NO and/or O2 on the Cu2+ Species in Cu-ZSM-5 : An EPR Study. In: Journal of Catalysis. 2000 ; Vol. 190, No. 2. pp. 352-363.
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AB - Two Cu2+-loaded ZSM-5 zeolites prepared by ion exchange from liquid solution (LS) and solid-state reaction (SR) are studied by EPR after vacuum treatments at several temperatures, Tv, up to 413 K and subsequent NO and/or O2 adsorption. In addition to the changes in Cu2+ coordination upon dehydration, from octahedral to square pyramidal and planar, outgassing produced in sample LS a decrease of the Cu2+ EPR signal, initiated by brief outgassing at 298 K and reaching a maximum (ca. 75% of the total copper not detected) for Tv=383 K. This is ascribed to fast spin relaxation, due either to a ligand geometry effect or to the establishment of copper-copper interactions. Subsequent NO adsorption at 298 K generated (Cu-NO)+ complexes, apparently by reaction of square planar Cu2+ (possibly assisted by water or OH- still present), while NO and O2 coadsorption led to a large change, all copper now being EPR-visible either as a sharp signal for a square planar species or as a broad band due to spin-interacting Cu2+. For sample SR, the resolved Cu2+ EPR signals, representing ca. 25% of the total copper, behave similarly to those found in sample LS (except that their overall intensity decreases little upon outgassing), but most copper exists as Cu-oxide clusters giving a broad EPR signal. The latter, resulting from the solid-state preparation method, seem scarcely reactive on adsorption of NO or NO+O2; they may be connected with the lower catalytic activity in NO decomposition previously observed for this latter sample.

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