Stabilization of the ethane oxidation catalytic activity of Cu-ZSM-5

The state of isolated copper ions in Cu-ZSM-5 containing additions of La, Ce, and Co was monitored in-situ by ESR under flow conditions. Treatment by steam at 630°C for 17 h or high-temperature dry calcination at 850°C induce an irreversible change in coordination for practically all square-planar Cu²⁺ ions in mono-cationic Cu-ZSM-5 without agglomeration or encapsulation of the isolated ions. All Cu²⁺ ions remain accessible to gas-phase molecules, but the catalytic reactivity of these altered copper sites decreases drastically. A stabilizing effect is noted for samples modified by a relatively large amount, ca. 5.0 wt.-%, of multivalent rare-earth ions La or Ce. Here a part of the copper ions (20–30%) preserves the parent square-planar Cu²⁺ state even after calcination at 850°C for 0.5 h. The effect of ca. 1% La or Ce is much less pronounced. The catalytic activity in the complete oxidation of ethane correlates well with the number of square-planar cupric cations retained by the samples after different treatments. The introduction of cobalt sharply increases the ethane oxidation activity of samples calcined at 500–650°C.