Lz. Gao et Ct. Au, Studies on the redox behaviour of La1.867Th0.100CuO4 and its catalytic performance for NO decomposition, CATAL LETT, 65(1-3), 2000, pp. 91-98
La1.867Th0.100CuO4 was prepared by means of the citric acid complexing meth
od. The reduction-oxidation (redox) properties of this composite oxide have
been investigated by using the XRD, TGA, EPR, TPD, and SEM methods. The fr
esh (non-reduced) La1.867Th0.100CuO4 catalyst is single phase with tetragon
al K2NiF4-type structure. There were three reduction steps observed over La
1.867Th0.100CuO4 in the temperature ranges of 25-100, 100-300, and 300-500
degrees C, respectively. After reduction at 300 degrees C, the material sti
ll retained its original single phase but there were oxygen vacancies gener
ated in the lattice. After reduction at 500 degrees C, it decomposed to a m
ixture of oxides. In the course of reduction, trapped electrons were genera
ted. During the oxidation of the reduced sample, O-2(-) was detected. Appar
ently, oxygen vacancies are able to stabilise O-2(-) on the surface of the
-1ptcatalyst. NO adsorption on both the fresh and reduced La1.867Th0.100CuO
4 samples generated NO radicals and O-2(-) species. On a La1.867Th0.100CuO4
sample reduced at 300 degrees C, [O2NO2](2-) was generated in NO adsorptio
n and decomposed to N-2 and O2- at ca. 730 degrees C. After reduction, the
O2- inside the La1.867Th0.100CuO4 lattice became more mobile and participat
ed in the decomposition of [O2NO2](2-). The fresh (non-reduced) La1.867Th0.
100CuO4 sample with cation defects in its lattice shows higher NO decomposi
tion activity than the fresh La2CuO4 sample in which there are no cation de
fects. The 300 degrees C-reduced La1.867Th0.100CuO4 with cation defects and
oxygen vacancies is more active than the fresh one for NO decomposition. T
he redox action between Cu+ and Cu2+ is an essential process for NO decompo
sition.