Computational Studies of the Adsorption Configurations and Dehydrogenation Mechanisms of Ethanol on the Rh/γ-Al2O3(110) Surface

[[abstract]]We applied periodic density-functional theory (DFT) to investigate the adsorption configurations and decomposition paths of ethanol on a Rh/γ-Al2O3(110) surface. Adsorption of ethanol onto a Al atom in the surface performs a larger adsorption energy than it adsorbed onto a Rh atom. But it is well known that the acidic support, γ-Al2O3 promotes dehydration of ethanol to ethylene. Therefore, we consider another ethanol adsorption configuration for the calculation of ethanol dehydrogenation pathways. In this configuration, ethanol adsorbed onto a Rh via α-cabon, two α-hydrogen atoms from ethanol are first eliminated; the barriers for abstraction of this two α-hydrogen atoms are calculate to be 2.59 and 7.35 kcal/mol, respectively. The dehydrogenation continues with the loss of one hydrogen from the O-H, forming an intermediate species CH3C(a)O + 3H(a), for which the successive barrier is 10.13 kcal/mol. Cleavage of the C-C bond occurs at this stage with a dissociation barrier Ea = 12.06 kcal/mol, to form C(a)H3 + C(a)O + 3H(a). The aforementioned reaction mechanism was also proposed and discussed by experiment.