Catalysis by Supported Metal Crystallites from Carbonyl Clusters. II. Catalytic Ethanol Synthesis from CO and H2 under Atmospheric Pressure over Supported Rhodium Crystallites Prepared from Rh Carbonyl Clusters Deposited on TiO2, ZrO2, and La2O3

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Abstract
Ethanol was catalytically produced in the CO–H2 reaction under atmospheric pressure and at 150–250 °C over rhodium crystallite catalysts prepared from Rh carbonyl cluster compounds highly dispersed on La2O3, TiO2, and ZrO2. The activity and selectivity of ethanol formation depend on the kind of metal carbonyl cluster and metal oxide used as inorganic carriers. The catalysts prepared by the pyrolysis of smaller Rh carbonyl clusters such as Rh2(C5H5)2(CO)3, Rh4(CO)12, and Rh6(CO)16 on La2O3, TiO2, and ZrO2 show higher selectivity of the oxygenated products containing ethanol (main), acetaldehyde, and methanol. The ethanol contents in the oxygenated products increased considerably above 200 °C over the catalysts. CeO2 and ThO2 were also employed in the preparation of the pyrolysed catalysts to disperse the Rh carbonyl clusters, which catalyses the ethanol formation in the CO–H2 reaction at atmospheric pressure.