A more efficient copper-ion-exchanged ZSM-5 zeolite for N-2 adsorption at room temperature: Ion-exchange in an aqueous solution of Cu(CH3COO)(2)

Citation
Y. Kuroda et al., A more efficient copper-ion-exchanged ZSM-5 zeolite for N-2 adsorption at room temperature: Ion-exchange in an aqueous solution of Cu(CH3COO)(2), PHYS CHEM P, 3(7), 2001, pp. 1383-1390
Citations number
53
Language
INGLESE
art.tipo
Article
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
ISSN journal
1463-9076 → ACNP
Volume
3
Issue
7
Year of publication
2001
Pages
1383 - 1390
Database
ISI
SICI code
1463-9076(2001)3:7<1383:AMECZZ>2.0.ZU;2-F
Abstract
The copper-ion-exchanged ZSM-5 type zeolite, prepared by ion-exchange in an aqueous solution of Cu(CH3COO)(2) and evacuation at 873 K, gives a distinc tive IR band at 2151 cm(-1) due to the adsorbed CO species. More efficient adsorption of N-2 was exhibited by this sample, compared with samples prepa red by other methods, implying site-selective ion-exchange in the preparati on process. On the basis of X-ray absorption near-edge structure (XANES) sp ectra the exchanged copper ion was proved to be in a monovalent state; one of the splitting strong bands, due to the 1s-4p(z) transition of the monova lent copper ion, loses its intensity on N-2 adsorption. The extended X-ray absorption fine structure (EXAFS) spectral pattern around the copper ion al so changed on N-2 adsorption and a shoulder appeared at around 1.5 Angstrom (no phase-shift correction), in addition to the strong band at around 1.65 Angstrom (no phase-shift correction). It was concluded that the monovalent copper-ion-exchanged site giving the 2151 cm(-1) band due to the adsorbed CO species is the active site for specific N-2 adsorption. A first principl es calculation was carried out with the object of finding the most appropri ate model for the CO species adsorbed on the exchanged copper ions in ZSM-5 . The data obtained suggest that a three-coordinate copper ion bonded to th ree lattice oxygen atoms adsorbs CO to give the 2151 cm(-1) band. A pseudo- planar structure including the monovalent copper ion bound to three oxygen atoms is assumed to change to a pseudo-tetrahedral arrangement on N-2 adsor ption. Such a site-selectively ion-exchanged substance has potential for th e development of materials for N-2 separation or fixation and activation ca talysts, as well as for the analysis of NO-decomposition sites.