By GEANKOPLIS CHRISTIE J.
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Extra info for Transport processes and unit operations
50 eV for the sites of Oa, Ob, and Oc, respectively. , 2009b): First, the relaxation is indeed Computational Rare Earth Catalysis 47 largely local for the Ob vacancy; the local relaxation energy accounts for $85% of the total relaxation energy. Second, the local relaxation at the site of Ob is much larger than those at the sites of Oa and Oc. Third, compared with the bond energy term, the local relaxation gives larger differences between Ob and Oa/Oc. Overall, one can conclude that the structural relaxation is the dominating term in determining why the O vacancy is favored to form at the Ob site rather than Oa and Oc.
However, it should also be noted that once the bent CO2 species occurs at the surfaces, carbonate formation can compete with the CO2 desorption. 35 eV. We can also understand the reactivity of carbonate formation from a geometric point of view. As we have presented, the adsorbed CO2 has a bent structure, indicating that the C gives a clear dangling bond. At CeO2(110), an active O3c on the neighboring row exists just beside the CO2 and it can be easily involved in the interaction with the dangling bond for carbonate formation.
54 eV lower than that of pure CeO2, in consistence with the experimental observations. , 2009a). Accordingly, EfV can be also decomposed into two terms: EfV ¼ Ebond þ Erelax in which Ebond is the energy required to remove the O with fixed bulk structure, and Erelax is the energy gained from the structural relaxation of the bulk in the presence of an O vacancy. 13 Variations of O vacancy formation energies, EfV, and related electrostatic (Ebond) and structural relaxation (Erelax) terms with respect to ZrO2 molar content in Ce1ÀxZrxO2.
Transport processes and unit operations by GEANKOPLIS CHRISTIE J.