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Hydrogen is suggested to come from the spillover from copper 42 The last step is the rapid hydrolysis of the surface methoxy to form the product methanol and restore the surface OH species required for the adsorption of the next CO 2 The water-gas shift reaction occurs predominantly on Cu and it is not affected by the presence of zr0 2 The suppressed rate of methanol formation over Cu on Zr02 from CO as compared to CO 2 is ascribed to the absence of water formation, which prevents the more facile release of methoxy by hydrolysis Hydrogenation of formates detected on Cu on Ti0 2 was also observed to occur 43 According to results coming from Baiker's group, the water-gas shift reaction plays a crucial role in CO 2 hydrogenation. 3 44-46 In the presence of surface hydroxyl groups, that is, over a prereduced catalyst, CO 2 is converted to surface carbonate, which is first reduced to yield adsorbed CO and water Methanol is then generated via surface-bound formaldehyde and methoxy species, which is released from the surface as a result of hydrogenolysis or protolysis In contrast to the suggestion of Bell, surface formate is believed to be an intermediate for methane formation not involved in the reduction of CO 2 The activity of traditional ZnO-based catalysts may be improved by using new preparation methods Cu-ZnO-AI 20 3 catalysts prepared by a new oxalate gel precipitation exhibited higher activity in CO 2 reduction than did those made by coprecipitation, which was attributed to the isomorphous substitution of Cu and Zn. 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