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3.5. Mechanisms for methanol steam reforming
Pour et al. [39] suggested that methanol conversion in the presence of water follows two steps. The first is methanol decomposition: CH3OH → CO + 2H2 (9) The second is the water gas shift reaction: CO + H2O → CO2 + H2 (8)

More recently, Takezawa and Iwasa [40], on the basis of finding formaldehyde and formic acid intermediates, has proposed a new pathway for methanol steam reforming over copper-based catalysts:

CH3OH → HCHO + H2 (10)
HCHO + H2O → HCOOH + H2 (11)
HCOOH → CO2 + H2 (12)
2HCHO → CH3OCHO (13)
CH3OCHO → CH3OH + CO (14)
CO + H2O → CO2 + H2 (8)

It is clear from Fig. 5 that the presence of Co enhanced the activity for the MSR. Furthermore, it can be
seen from Fig. 6 that although the selectivity for CO formation was greater than that over pure skeletal copper, the selectivity for CO2 formation was in excess of 80% even when the Co concentration was more than 1 wt.%. From Fig. 4 it can be seen that skeletal copper containing this level of Co had negligible activity for the water gasshift reaction. Therefore, we can conclude that the mechanism proposed by Pour et al. [39] is not correct for the copper-catalyzed MSR reaction and that the mechanism proposed by Takezawa and Iwasa [40] is more plausible. Furthermore, it appears that the mechanism represented by Eqs. (10)–(12) predominates for copper-based catalysts and that the mechanism represented by Eqs. (10)-(8) is less dominant.

The presence of Cr2O3 and ZnO favored the WGS reaction (Eq. (8)) and accounted for the reduced selectivity for CO formation, whereas the presence of Co made the Cu surface inactive for the WGS reaction, thereby accounting for the observed increase in CO selectivity. The results of this study are consistent with Takezawa and Iwasa’s [40] explanation of the mechanism for the MSR reaction and the findings of Jiang et al. [41] using a Cu-ZnO/Al2O3 catalyst.