3.2. Catalytic activity and selectivity
The performance of the resulting catalysts for methanol synthesis from CO2 hydrogenation is shown in Table 1. CO and methanol
are the only carbon-containing products under the reaction conditions and traces of methane can be detected when the temperature
is higher than 513 K. It can be seen that the CO2 conversion increased with the decrease of urea amount and reached a maximum
for sample 50-CZZ. The trend is similar to that of crystallite size of
CuO species and active surface area of Cu of the catalysts. This is
because smaller crystallite size of CuO species and higher active
surface area of Cu lead to more active catalysts[16,18]. At the same
time, the reduction temperatures of CuO showed in the TPR profiles provide a strong evidence for the sequence of activity. On
the other hand, it is noteworthy that the CH3OH selectivity increased monotonically with the increase of urea amount although
the enhancement was not significant. It can be ascribed to partial
transformation from t-ZrO2tom-ZrO2 occurred as the urea amount
increased during catalyst preparation which demonstrated by the
XRD spectra. The methanol selectivity overm-ZrO2-supported catalysts is higher than that overt-ZrO2-supported catalysts. Similar
results for CO hydrogenation had been reported by Rhodes and Bell
[19]. As seen in Table 1, 50-CZZ catalyst exhibits the highest yield
of methanol among all the catalysts investigated here.
The catalytic performances of CZZ catalysts with the same composition prepared by carbonate and oxalate co-precipitation methods as well as combustion method are shown inFig. 3, for the
purpose of comparison. It is obvious that the catalysts prepared
by combustion method are more active for methanol synthesis
from CO2 hydrogenation. On the other hand, the temperature at
which the maximum methanol yield obtained over the catalyst
prepared by combustion method was evidently lower than those
over the catalysts prepared by carbonate and oxalate co-precipitation methods, indicating that the former has better low temperature activity. The high activity described above of the CZZ
catalyst prepared by combustion method may be due to the high
temperature treatment during combustion synthesis process,
which persists for a few minutes and renders rapid quenching effect[20]resulting in a more favorable interaction between copper
species and ZnO, ZrO2.