| Sumario: | Ab initio molecular orbital theory and density functional theory calculations have been used to study the three-stage zeolite-catalyzed hydrogenation of CO to methanol and the hydrogenation of CH to ethane, with the aim of designing an effective zeolite catalyst for these reactions. Both Bronsted acid (XH) and alkali metal (XM) sites in model zeolites (-X-Al-XH- or -X---Al--XM-) have been examined, It is found that appropriately designed zeolites can provide excellent catalysis for these reactions, particularly for the hydrogenation of CO, HCOH and CHO, with uncatalyzed barriers of more than 300 kJ mol being reduced to as little as 17 kJ mol (in the case of CHO). The reaction barrier depends on the acidity of the XH moiety or the nature of the metal cation M in the XM moiety, and the basicity of the adjacent X group in the catalyst. For a catalyst based on alkali metal zeolites (XM), the catalytic activity is relatively insensitive to the nature of X in the XM group. As a result, the catalytic activity for these types of zeolites increases as X becomes more basic. We propose that alkali metal zeolites with Ge and N incorporated into the framework could be very effective catalysts for hydrogenation processes.
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