화학공학소재연구정보센터
Journal of Catalysis, Vol.190, No.2, 352-363, 2000
Influence of the preparation method, outgassing treatment, and adsorption of NO and/or O-2 on the Cu2+ species in Cu-ZSM-5: An EPR study
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, T-v, up to 413 K and subsequent NO and/or O-2 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 T-v = 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 O-2 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 + O-2; they may be connected with the lower catalytic activity in NO decomposition previously observed for this latter sample. (C) 2000 Academic Press.