Top view and side view (inserted) of the calculated TS structures of (a) dissociation and (b) formation through on Rh(111). Red (gray), light blue (black), and deep blue (gray, surface layer) ball represent O, N, and Rh, respectively.
The standard free energy profiles of NO oxidation on Pt(111), Ir(111), and Os(0001) surfaces at (the top, middle, and bottom curves. respectively). The entropy effects of gas-phase , NO, and are included, in which ; ; . The dash lines indicate the reaction pathway at .
The volcano curve, i.e., plotting of the logarithmic TOF, log(TOF), of NO oxidation against the oxygen chemisorption energy. It should be noted that the oxygen chemisorptions energy is calculated at , including the contribution of entropy of oxygen molecule.
Decomposition of the volcano curve of NO oxidation according to Eq. (7). As increases, increases approximately linearly [the blue (linear) line], while the term of free site— decreases according to a conic curve [the red curve (line b)]. The competition between these two factors gives rise to the volcano curve. Dashed curves are illustrations of how the curvature of affect the peak position of volcano curves.
Calculated adsorption energies on the most stable sites, and the barriers for the elementary reactions on surfaces of Ru, Rh, Pd , Os, Ir and Pt . The units are eV.
Kinetic data for NO oxidation catalyzed by Ru, Rh, Pd, Os, Ir, and Pt surfaces. The rate and equilibrium constants are derived from the DFT results with the entropy effect included; the other kinetic parameters are numeric results of Eq. (6) under the typical experimental condition , , , .
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