C. Kappenstein et al., COPPER-ZINC OXIDE CATALYSTS .4. THERMAL-TREATMENT IN AIR, ARGON AND HYDROGEN AND XRD STUDY OF NEW BIMETALLIC PRECURSORS-DIRECT FORMATION OFALLOYS, Thermochimica acta, 279, 1996, pp. 65-76
Four new Cu-Zn bimetallic precursors of model catalysts for methanoliz
ation of syngas, Zn(NH3)(2)Cu(CN)(3) (ZCA), [Zn(en)(3)](6)[Cu-5(CN)(17
)]. nH(2)O (n = 8.4) (ZCE3), [Zn(en)] [CCu(CN)(3)] (ZCE1) and [Zn1-xCu
x(en)] [CCu(CN)(3)] (ZCCE1), were thermally treated in air, hydrogen a
nd argon atmosphere between 200 and 900 degrees C. The calcinations in
air yield firstly a mixture of cyano-ligand-containing compounds whic
h transform at temperatures above 300 degrees C to CuO and ZnO; the cr
ystallite size of both oxides increases with temperature. The reductio
n in hydrogen at 300 degrees C gives zinc cyanide and metallic copper
which are converted at 450 degrees C mainly to beta'-brass including s
ome alpha- and gamma-alloys. The thermal treatment in argon displays t
he very high thermal stability of zinc cyanide to 900 degrees C and fo
rmation of copper or alpha-CuZn alloy. Only the hydrogen treatment avo
ids the segregation of both metallic elements. The results are discuss
ed on the basis of thermodynamic data.